structural studies of some pharmaceutical and...

CHAPTER IV

Introduction to organic picrates

Cinnarizinium dipicrate

Enrofloxacinium picrate

Etoricoxibium picrate

Levocetirizinium dipicrate

Lomefloxacinium picrate

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Section 4.1

Introduction to organic picrates

Introduction

Picric acid is the chemical compound formally called 2,4,6-trinitrophenol

(TNP) is a pale yellow, odorless crystal that is slightly soluble in water. When

hydrated, it is typically harmless but when dry can be a powerful explosive. Picric

acid was widely considered suitable to with stand the shock of firing in conventional

artillery and picric acid is highly sensitive to heat, shock and friction and,

additionally, is a toxic substance by all modes of entry (i.e., inhalation, ingestion,

dermal contact). But shock sensitivity sometimes caused detonation in the artillery

barrel at the time of firing. Picric acid is highly reactive with a wide variety of

materials (e.g., concrete, plaster, amines, bases, and metals such as lead, zinc, copper,

and mercury) to form picrate salts, which are more reactive and shock sensitive than

the acid itself. Picric acid was used in the battle of Omdurman, second Boer war, the

Russo-Japanese war, and world war I. It is also present in many laboratories, for use

as a chemical reagent.

OH

O2N NO

2

NO2

(TNP)

Picric acid is used primarily in the manufacture of explosives and as an

intermediate in dye manufacturing. Water is added to picric acid to act as a

desensitizer. The wetted product is significantly less shock sensitive than the dry acid.

Picric acid is highly reactive with a wide variety of chemicals and extremely

susceptible to the formation of picrate salts. Many of these salts are even more

reactive and shock sensitive than the acid itself.

The special characteristics of the picrate anion as a versatile counter-ion for

cation complexation are demonstrated by crystal structures. On the basis of the

experimental data reported in the literature a categorization into different modes of

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383

picrate cation interactions is proposed together with the corresponding nomenclature.

The results of the present study and the analysis of the picrate versatile interactions

may be used for various scientific and commercial applications since picrate is

commonly used as a counter-ion in many systems involving extraction and transport

of alkali and alkaline earth metal cations. The data presented here should also be

considered for systems involving picrate as counter ion where high efficiency and

selectivity towards specific ion are desired. Such systems may be significantly

affected from the high diversity of both the coordination and geometry of the picrate-

cation interactions.

In few structures, due to conformational constrains, the picrate is involved in

the coordination of the cation as monodentated ligand via o-nitro or p-nitro oxygens.

Experimenta1 evidences to the coordination ability of the nitro group to alkali metal

cations are known. Therefore picrate is a versatile mono/bi/tri dentate ligand. It is an

integral part of complexes of alkali and alkaline earth metal cations with natural and

synthetic ion ophores. Another important characteristic of aromatic poly nitro

compounds is their ability to form stable complexes with aromatic hydrocarbons,

especially those that are substituted with alkyl groups or are otherwise expected to

have electron-donating properties. This behavior is very commonly observed with

picric acid, and the complexes therefore are often nicely crystalline solids, which are

useful for the separation, purification, and identification of organic compounds.

Picric acid forms crystalline picrates with various organic molecules, and such

picrates are convenient for identification and qualitative analysis of the organic

compounds. Picric acid forms charge transfer molecular complexes with a number of

aromatic compounds such as aromatic hydrocarbons, amines etc. through electrostatic

or hydrogen bonding interactions (In et al., 1997 & Zaderenko et al., 1997) and

aromatic heterocyclic compounds have been investigated. Since it is useful to

understand the nature of structures of picrates of basic compounds, it is advantageous

to study the interaction of drug molecules with picric acid. Now, it has become clear

that the picrates of basic aromatic hydrocarbons are formed through π -bonding (π-π

interaction), while picrates of aromatic heterocycles are formed through ionic and

hydrogen bonding or π-π interaction. The crystal structures of a large number of

picrate salts and picric acid complexes have been studied to understand the

384

conformational features and charge transfer processes (Li et al., 2009, Nagata et al.,

1995; Sivaramkumar et al., 2010, Smith et al., 2004; Goto et al., 2004). Picric acid

has been also used in the characterization of organic bases because of the ease of

crystallization and hence purification when picrate derivatives are produced (Pascard

et al., 1982; Pearson et al., 2007; Shakir et al., 2009).

Picric acid (2,4,6-trinitrophenol) is a strong acid because of resonance

stabilization of the phenoxide anion due to the presence of the nitro substituents. It is

known to form salts with both aromatic and aliphatic amines (Thewalt & Bugg, 1972;

Takayanagi et al., 1996; Anitha et al., 2005).

Picric acid could also be an additional compound which picric acid forms with

many aromatic hydrocarbons, aromatic amines, aliphatic amines, alkalines, and other

compounds (Smith & March, 2007). Picric acid form crystalline picrates with various

organic molecules and such picrates have been very available for the identification

and qualitative analysis of the corresponding organic compounds. It is clear that the

picrates of the fundamental aromatic hydrocarbons are formed through π-π interaction

as well as those of the hetero aromatic compounds. Corresponding picrates are formed

through ionic and hydrogen bonding. (Yamaguchi et al., 1988 & Goto et al., 1992).

Picric acid forms stable picrates with various organic molecules through π -

bonding or ionic bonding, and such picrates have been very useful for identification

and qualitative analysis, as it seemed desirable to determine the crystal structures and

the bonding mode of picrates of basic organic compounds (Takayanagi et al., 2004).

The crystal structure studies of picric acid alone is reported by several authors

(Duesler et al., 1978; Soriano-Garcia et al., 1978; Srikrishnan et al., 1980 and

Narayana et al., 2007).

The crystal structures of organic and inorganic picrates is vast, where in more

than 700 picrates have been reported in CSD as on December 2011. Some important

organic picrates, excluding inorganic picrates are reported in this section. The crystal

and molecular structure studies of picric acid-1-bromo-2-aminonaphthalene complex

(Carstensen-Oeser et al., 1968) α-naphthol picrate (Rastogi & Singh, 1970), serotonin

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385

picrate monohydrate (Thewalt & Bugg, 1972), 3,5,7-triphenyl-4H-1,2-diazepine

picrate (Gerdil, 1972), cytosine picrate (Einspahr et al., 1974), carbamoylcholine

picrate picric acid (Jensen, 1975), triphenylene - picric acid complex (Herbstein

Kaftory, 1975), naphthalene - picric acid complex (Herbstein Kaftory, 1975a),

pyridine picrate (Talukdar & Chaudhuri, 1976), anthracene-picric acid (Herbstein &

Kaftory, 1976), benzene picric acid (Herbstein et al., 1976), ethyl n-(n'-

methylbenzimidoyl) benzimidate picrate (Jones & Kennard, 1977), 2-thiocytosine

picrate (DeLucas et al., 1977), picric acid (Soriano-Garcia et al., 1978), promethazine

picrate (Narayana achar & Shashidhara Prasad, 1979), bupranolol picrate (Dubost et

al., 1981), N,2a-dimethyl-8b-t-butyl-cis-decahydroquinoline picrate (Onan &

Vierhapper, 1984), N-benzyl-cis-4,5-tetramethylenetetrahydro-1,3-oxazinium picrate

(Fulop et al., 1984), 2,2-diethyl-1,2-dihydro-4,6-dimethylpyrimidinium picrate

(Ferguson et al., 1984), p-hydroxyphenyl-thiophenium picrate (Kalinin et al., 1984),

1,2,3-trihydro-6-(p-hydroxyphenyl)-7-methyl-indolizinium picrate (Yu et al., 1985),

disordered structure of picric acid-naphthalene (Banerjee & Brown, 1985), kinetin

picrate (Soriano-Garcia et al., 1985), dimethylammonium picrate (Walkinshaw,

1986), dipicrates of 2-(2-amino-4-imidazolyl)ethylamine, its 5-methyl derivative and

n,n-dimethyl-2-(2-amino-1,3-thiazol-5-yl)ethylamine (Nardelli et al., 1987), 4-(3-

indolyl)butyric acid-picric acid complex (Soriano-Garcia et al., 1987),

benzoquinolizinium picrate monohydrate (Wang & Jones, 1987), 1,2,3,4-tetrahydro-

1,4-dimethylisoquinolinium picrate (Watson et al., 1988), 3-methyl-4-pyrimidonium

picrate (Kasende et al., 1988), 3-hydroxy-1-t-butyl-1,2-dihydropyrrolium picrate

(Blake et al., 1988), phenanthrene: picric acid complex (Yamaguchi et al., 1988),

acetylcholine picrate and methoxycarbonylcholine picrate hemihydrate (Frydenvang et

al., 1988), thiamine picrate (Kim et al., 1988), cis-1,2-di-N-piperidinocyclopentane

dipicrate (Fraenkel et al., 1989), 7,16-dimethyl-7H+, 16H

+-1, 4,10, 13-tetrathia-7,16

diazoniacyclooctadecane dipicrate (Blake et al., 1989), 6-bromo-2,3-dihydro-5,7-

dimethyl-1,4-diazepinium picrate and 6-bromo-2,3-dihydro-1,4-diazepinium picrate

(Ferguson et al., 1990), imidazole picrate (Soriano-Garcia et al., 1990), pyridinium

picrate (Takayanagi et al., 1990), ethyl 8-dimethylamino-1-naphthalenecarboxylate-

picric acid (Parvez & Schuster, 1991), benzene:picric acid complex (Takayanagi et

al., 1991), quinolinium picrate (Goto et al., 1992), 1,4-naphthoquinone picrate (Goto

et al., 1992), isoquinolinium picrate (Goto et al., 1992), muscarone picrate

(Frydenvang & Jensen, 1992), muscarine picrate (Frydenvang & Jensen, 1993), L-

tryptophan-picric acid (Ishida et al., 1993), 1:1 and 1:2 adducts of 1,8-bis

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386

(dimethylaminomethyl) naphthalene with picric acid (Brzezinski et al., 1993),

ethoxycarbonylcholine picrate hemihydrate (Frydenvang et al., 1994), glycine picrate

(Kai et al., 1994), pyridinium picrate (Botoshansky et al., 1994), water and the picrate

anion in the solid state (Llamas et al.,1995), indole-3-acetamide picric acid (Nagata et

al.,1995), 3-amino-1-phenyl-4,5-dihydropyrazol-2-ium picrate (Claramunt et al.,

1995), 1,8-bis(dimethylamino)naphthalene picrate (Lopez et al., 1996), a 1:2 host-

guest complex of diaza-15-crown-5 with picric Acid (Saleh et al., 1996), aromatic

amine picrates (Takayanagi et al., 1996), imidazole-4-acetic acid-picric acid (In et al.,

1997), 4,6,8-trimethylazulene and picric acid (Nather et al., 1997), diethyl 2-

benzimidazol-1-ylsuccinate-picric acid (Zaderenko et al., 1997), anthranilic acid-

picric acid (In et al., 1997), dichloropicric acid (Chantooni Junior et al., 1997), 1-

amino-4-phenyl-2-(3,5-diphenylpyrazolyl)imidazolium picrate picric acid solvate

(Peters et al., 1998), picrates of o-xylene and p-xylene (Goto et al., 1998), p-Xylene

tris(picric acid) (Goto et al., 1998), betaine bis(imidazole picric acid) (Overgaard et al.,

1999), betaine bis(imidazole picric acid) (Overgaard et al., 2001), 1,10-diazonia-18-crown-

6-picrate (Chekhlov, 2001), 2-(4-hydroxyphenyl) ethylammonium picrate (Ohba & ito,

2002), n-methylmorpholine betaine with picric acid (Dega-Szafran et al., 2002), N-

carboxymethyl-N-methyl)morpholin-4-ium (4-methylmorpholin -4-ium)acetate picrate

hemihydrate (Dega-Szafran et al., 2002), L-prolinium picrate (Jin et al., 2003),

pyridinium-3-carboxamide picrate (Fang et al., 2003), 1-amino-3-methylnaphtho(1,2-

d)imidazolium picrate (Koroleva et al., 2003), 5,6-dihydro-2-methyl-4H-thieno[2,3-

f][1,2,4]triazolo[1,5-a]azepine picrate (Wang et al., 2003), 4-hydroxymethylimida-

zolium picrate (Du & Zhao, 2003), 2-aminobenzimidazolium picrate (El-Medani et

al., 2003), isonicotinamide picrate (Carvalho et al., 2003), 4-(hydroxymethyl)

imidazolium picrate (Du & Zhao, 2003), 4-dimethylaminopyridinium picrate (Vembu

et al., 2003), N-(2-aminoethyl)-2-hydroxybenzamide with picric acid (Yu et al.,

2003), l-prolinium picrate (Jin et al., 2003), hexane-1,6-diammonium dipicrate

dehydrate (Lin & Lu, 2004), L-valinium picrate (Anitha et al., 2004), DL-valine DL-

valinium picrate (Annavenus et al., 2004), β-alanine β-alaninium picrate (Anitha, et

al., 2004a), polymorph of anilinium picrate (Smith et al., 2004), 1-piperidineaceic

acid picrate (Dega-Szafran et al., 2004), adenosinium picrate (Goto, Kanno et al.,

2004), 2',6'-dimethoxyflavone picrate (Lago et al., 2004), 1-(2-imidazolio)-2,5,8-

trioxanonane picrate (Schuster et al., 2004), 4-ethyl-2,6-di-isopropyl-3,5-

dimethylpyridinium picrate (Balaban et al., 2004), L-methionine sulfoxide picrate

(Lherbet et al., 2004), 4,4'-bipyridinium dipicrate (Ma et al., 2005), norfloxacin

387

picrate (Hu & Yu, 2005), DL-phenylalanine DL-phenylalaninium picrate (Anitha &

Rajaram, 2005), L-asparaginium picrate (Anitha et al., 2005b), L-leucine L-leucinium

picrate (Anitha et al 2005), piperidinium picrate (Saminathan et al., 2005), 1-

dimethylammoniomethyl-6,8-dimethyl-2-phenyl-1,2 dihydroimidazo [1,2a]

[1,8]naphtha yridine picrate monohydrate (Muthamizhchelvan et al., 2005), 4,4'-

bipyridinium dipicrate (Ma et al., 2005), cyclohexylammonium picrate

(Muthamizhchelvan et al., 2005a), 5-amino-1-methyl-4H-tetrazolium picrate

(Lyakhov et al., 2005), 1-(4-methylpiperdinemethyl)-2-(4-bromophenyl)-6-methyl-8-

trifluoromethyl imidazo [1,2-a] [1,8] naphthyridinium picrate (Muthamizhchelvan et

al., 2005b), triethylaminium picrate (Muthamizhchelvan, et al., 2005c), 3-

methylanilinium picrate (Muthamizhchelvan, et al., 2005d), nicotinium picrate

(Anitha et al., 2005c), 3-(dimethylammonio) propanaminium dipicrate and

ethylaminium picrate (Muthamizhchelvan et al., 2005e), 2-chloroanilinium picrate

(Muthamizhchelvan et al., 2005f), 2,2,4-trimethyl-2,3-dihydro-5H-1,5-benzodiazepinium

picrate (Thakuria et al., 2006), 1,1'-methylenebis(4-methyl-1H-triazolium) dipicrate

(Jin et al., 2006), 1,2,4-triazolium picrate (Jin, et al., 2006a), 2-methylquinolinium-

5,8-dione-5-oxime picrate ethanol solvate (Majerz-Maniecka et al., 2006), α-

methylbenzylammonium picrate (Costero et al., 2006), 2-amino-4,6-

dimethylpyrimidinium picrate (Subashini et al., 2006), 1,2,4-triazolium picrate (Jin et

al., 2006), thiaminium picrate (Anitha et al., 2006), DL-methionine DL-methioninium

picrate (Anitha et al., 2006), diisopropylethylammonium picrate (Podoprygorina et

al., 2006), monoprotonated [2.2.2]cryptand picrate monohydrate (Refat et al., 2006),

pyridoxinium picrate (Anitha et al 2006a), L-prolinium picrate and 2-

methylpyridinium picrate (Anitha e. al.,2006b), L-asparaginium picrate (Srinivasan et

al., 2006), mixed 3,5-dinitrosalicylate(2-), partial 3,5-dinitrosalicylate(1-) and

picrate(1-) species in tris(piperidinium) bis(3,5-dinitrosalicylate) picrate monohydrate

(Smith et al., 2006), 1,1'-methylenebis(2,3-dimethylimidazolium) dipicrate (Li.,

2007), polymorphs of picryl bromide (Parrish et al., 2007), 2:1 complex of 2-

nitroaniline and picric acid (Saminathan & Sivakumar, 2007), promazinium picrate,

ethopropazinium picrate, mepazinium picrate, trifluoperazinium picrate,

chlorpromazinium picrate (Yathirajan et al., 2007; 2007a; 2007b; 2007c; 2007d),

dioxopromethazinium picrate (Harrison et al., 2007), imipraminium picrate (Harrison, et

al., 2007a), 1,3,7-trimethylxanthenium 2,4,6-trinitrophenolate (Chandramohan et al.,

2007), thiosemicarbazidium picrate monohydrate (Xie, 2007), amitriptylinium picrate

(Bindya et al., 2007), phenothiazine-picric acid (Harrison et al., 2007b), 2:1 complex

388

of 2-nitroaniline and picric acid and indole-picric acid (saminathan & Sivakumar, 2007;

2007a), 1:1 complexes of 4-methyl-morpholine-N-oxide and 3-picoline-N-oxide with

2,4,6-trinitrophenol & 3-methylpyridine-N-hydroxide picrate (Zukerman-Schpector et

al., 2007), 9-methyl-2-propyl-5,6-dihydro-4H-furo[2,3-f][1,2,4]triazolo[1,5-a]azepine

picric acid (Qingqing Meng, et al., 2007), desipraminium picrate monohydrate

(Harrison et al., 2007c), desipraminium picrate (Swamy et al., 2007), nevirapininium

picrate (Harrison, et al., 2007d), 8-hydroxyquinloinium picrate (Kumar &

Nagalakshmi, 2007), 2-aminopyrimidinium picrate (Narayana et al., 2008), 5-amino-

1-methyl-1H-tetrazolium picrate (Klapotke & Sabate, 2008), L-valinium picrate

(Srinivasan et al., 2008), 3,3'-dibenzyl-2,2'-dimethyl-1,1'-methylenediimidazolium

dipicrate (Jin et al., 2008), L-valinium picrate (Martin Britto Dhas & Natarajan,

2008), caffenium picrate (Chandramohan et al., 2008), 1,1'-butane-1,4-diyl-

dibenzimidazolium picrate (Yan et al., 2009), phthalazin-1(2H)-one-picric acid

(Yathirajan et al., 2008), dibenzo-18-crown-6-picric acid-water (Saleh et al., 2008), 3-

benzyl-1-methylimidazolium picrate (Pi et al., 2009), gabapentinium picrate (Li et al.,

2009), 4-(2-chloroethyl) morpholinium picrate (Kant et al., 2009), 4-(4-

carboxybenzyl)-1-methylpiperazin-1-ium picrate (Li, et al., 2009a), 2-amino-4,6-

dimethoxypyrimidinium picrate and pyrimethaminium picrate dimethyl sulfoxide

solvate (Thanigaimani et al., 2009), 3-benzyl-1-methyl-1H-imidazol-3-ium 2,4,6-

trinitrophenolate (Pi et al., 2009a), haloperidol picrate (Jasinski et al., 2009), 4-((E)-

(2,4-difluorophenyl)(hydroxyimino) methyl)piperidinium picrate (Jasinski et al.,

2009a), 1-(2-methyl-5-nitrophenyl) guanidinium picrate (Jasinski et al., 2009b),

morpholinium picrate (Vembu & Fronczek, 2009), 4-nitroaniline-picric acid (Li,

2009b), propiverinium picrate (Jasinski et al., 2009c), 3-chloro-5-[3-(dimethylamino)

propyl]-10,11-dihydro-5H-dibenz[b,f]azepinium picrate (Jasinski et al., 2010a),

imatinibium dipicrate (Jasinski et al., 2010b), 5,7-dimethyl-2,3-dihydro-1H-1,4-

diazepin-4-ium picrate (Jasinski et al., 2010c), 4-tert-butylpyridinium picrate

(Ramesh et al., 2010), 2-Amino-4-methoxy-6-methylpyrimidin-1-ium picrate

(Jasinski et al., 2010d), opipramol dipicrate (Jasinski et al., 2010e), 4-

aminopyridinium picrate (Ramesh et al., 2010a), orphenadrinium picrate picric acid

(Fun et al., 2010), 4-(4-chlorophenyl)-4-hydroxypiperidinium picrate dimethyl

sulfoxide solvate (Fun et al., 2010a), pefloxacinium picrate (Fun et al., 2010b), 1,1'-

butane-1,4-diylbis(1H-imidazol-3-ium) picrate (Shouwen et al., 2010), 2-

methylanilinium picrate (Gao-Xiag Meng et al., 2010), 1-hydroxy-4-aza-1-

azoniabicyclo[2.2.2]octane picrate (Jing-Mei Xiao., 2010), 2-aminopyridinium picrate

389

(Sivaramkumar et al., 2010), 3-aminopyridinium picrate (Yan-jun Li et al., 2010),

fluconazolium picrate (Dutkiewicz et al., 2010), fluphenazinium dipicrate

dimethylsulfoxide solvate (Dutkiewicz et al., 2010a), 2-aminoanilinium picrate (Rong

Peng & Yanping Zhao 2010), isonipecotamide picrate (Smith & Wermuth, 2010),

2,3,5,6-tetramethylpyrazine-1,4-diium bis(picrate) (Sawka-Dobrowolska et al., 2010),

1,1'-butane-1,4-diylbis(1H-imidazol-3-ium) picrate (Jin et al., 2010), pyridinium

picrates (Stilinoci & Kaitner, 2011), orphendrinium picrate (Jasinski et al., 2011),

benzotriazolium picrate (Zeng et al., 2011), 1-methylpiperazine-1,4-di-ium dipicrate

(Dutkiewicz et al., 2011), 2-methylimidazolium picrate (Dutkiewicz et al., 2011a), 4-

(1-cyclopropyl-3-carboxy-6-fluoro-4-oxo-1,4-dihydroquinolin-7-yl)-1-ethylpiperazin-

1-ium 2,4,6-trinitrophenolate (Jasinski et al., 2011a), ethane-1,2-diaminium dipicrate

dehydrate (Jaisinski et al., 2011b), phenylazoaniline picrate (Smitha et al., 2011),

oxonium picrate (Jin et al., 2011), picric acid- 2,4,6-trichloroaniline (Wang, 2011),

triprolidinium dipicrate (Dayananda et al., 2011), 1-methyl-2-({[(1-methyl-1H-

benzimidazol-2-yl)methyl] (phenyl)amino}methyl) 1H-benzimidazol -3-ium picrate (Liu

et al., 2011), 4-[bis(4-fluorophenyl)methyl]piperazin-1-ium picrate (Betz et al., 2011),

(E)-5-(2-chlorophenyl)-7-ethyl-2-oxo-2,3-dihydro-1H-thieno[2,3-e][1,4]diazepin-4-

ium2,4,6-trinitrophenolate (Betz et al., 2012) and tramadolium picrate (Siddaraju et al.,

2012) have been reported.

It is of great importance to study the crystal structures of picrates of drug

molecules, because of various hydrogen bonding interactions that are possible in the

solid state. In this connection, the present chapter describes the synthesis, crystal and

molecular structure studies of levocetirizinium dipicrate, etoricoxibium picrate,

enrofloxacinium picrate, cinnarizinium dipicrate and lomefloxacinium picrate.

* * * * *

390

Section 4.2

Crystal structure studies of cinnarizinium dipicrate

Abstract

In the cinnarizinium dication of the title compound {systematic name:1-

diphenylmethyl- 4-[(2E)-3- phenylprop-2-en-1- yl]piperazine- 1,4 -diiumbis (2,4,6-

trinitrophenolate)}, C26H3ON22+

2C6H2N3O7-, the piperazine group is protonated at both

N atoms and adopts a slightly distorted chair conformation. Strong N—H···Ohydroxy

cation–anion hydrogen bonds link the dication and two anions. In the cation, the (2E)-

3-phenylprop-2-en-1-yl fragment is disordered over two positions in a ratio of 0.586

(4): 0.414 (4). Two nitro groups in one anion and three in the other one demonstrate

rotational disorder. The crystal packing is stabilized by weak intermolecular π–π

[centroid–centroid distances = 3.844 (7), 3.677 (9), 3.825 (5), 3.634 (2) and 3.729 (7)

Å], C—H···π and C—H···O interactions.

The title compound, crystallizes in a monoclinic, space group P21/c with a =

15.1987(2) Å; b = 10.09128(17) Å; c = 25.0724(3) Å; α = 25.0724(3)°; β =

95.9171(14) °; γ = 90°; V = 3824.97(10) Å3; Z = 4; Dcal = 1.436 Mg/m

3 at T = 295(2)

K. The structure was solved by direct methods and refined by full-matrix least-

squares procedures to final R = 0.0950 and wR2 = 0.2766 using 7319 reflections.

Introduction

Cinnarizine is an antihistamine which is mainly used for the control of nausea

and vomiting due to motion sickness. Cinnarizine could be also viewed as a nootropic

drug because of its vasorelaxating abilities (due to calcium channel blockage), which

happen mostly in brain. Cinnarizine can be used in scuba divers without an increased

risk of central nervous system oxygen toxicity. The crystal structures of some related

compounds viz., cinnarizine (Mouille et al., 1975), cyclizine hydrochloride (Bertolasi

et al., 1980) cinnarizinium 3,5-dinitrosalicylate (Dayananda et al., 2012) and

cinnarizinium picrate (Song et al., 2012) have been reported. In continuation of our

work on the picrates of pharmaceutical compounds, we have reported the

cinnarizinium dipicrate.

391

In view of the importance of the title compound, (10), the crystal structure is

reported in this section.

O

NO2

NO2O2NN NH

H2

(XX)

Chemical structure of the title compound

Experimental

Cinnarizine (3.68 g, 0.01 mol) and picric acid (4.58g, 0.02 mol) were

dissolved in hot acetonitrile and dimethyl sulphoxide (80:20 v/v) solution and stirred

over a heating magnetic stirrer for few minutes (330 K). The resulting solution was

allowed to cool slowly at room temperature. X-ray quality crystals of the title

compound appeared after a few days. (m.p.: 481- 483 K).

The reaction scheme is shown below.

O

NO2

NO2O2NN NH

H2

OH

NO2

NO2O2NN N

Acetonitrile + DMSO

+ 2

Reaction scheme

392

Refinement

Carbon atoms C18–C26 are disordered (0.586 (4) A: 0.414 (4) B). The oxygen

atoms on the N1A, N3A, N1B, N2B and N3B anion nitro groups are rotationally

disordered [O2AA & O3AA (0.68 (2)), O2AB & O3AB (0.32 (2)); O6AA & O7AA

(0.851 (14)), O6AB & O7AB (0.149 (14)); O2BA & O3BA (0.80 (2)), O2BB &

O3BB (0.20 (2)); O4BA & O5BB (0.951 (19)), O4BB & O5BB (0.050 (19)); O6BA

& O7BA (0.756 (8)), O6BB & O7BB (0.244 (8))] H1N and H2N were refined

isotropically. All of the remaining H atoms were placed in their calculated positions

and then refined using the riding model with Atom—H lengths of 0.93 & 0.98Å (CH),

or 0.97Å (CH2). Isotropic displacement parameters for these atoms were set to 1.19–

1.20 (CH, CH2) times Ueq of the parent atom. The highest residual peak of 1.24 eÅ-3

is

situated 1.16 Å from atom O1B.

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account

individually in the estimation of e.s.d.'s in distances, angles and torsion angles;

correlations between e.s.d.'s in cell parameters are only used when they are defined by

crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for

estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR

and goodness of fit S are based on F2, conventional R-factors R are based on F, with F

set to zero for negative F2. The threshold expression of F

2 > σ(F

2) is used only for

calculating R factors(gt) etc. and is not relevant to the choice of reflections for

refinement. R-factors based on F2 are statistically about twice as large as those based

on F, and R- factors based on ALL data will be even larger.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis

PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to

solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:

SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008);

software used to prepare material for publication: SHELXTL.

393

Results and discussion

Crystal data and structure refinement details are given in Table 4.1. Atomic

coordinates of the non-hydrogen atoms with their equivalent isotropic displacement

parameters are presented in Table 4.2. The anisotropic displacement parameters are

listed in Table 4.3. The bond lengths and angles involving the non-hydrogen atoms

are given in Tables 4.4 and 4.5 respectively. Table 4.6 lists atomic coordinates of the

hydrogen atoms. The bond lengths and bond angles involving the hydrogen atoms are

listed in Tables 4.7 and 4.8. The torsion angles are presented in Table 4.9. Table 4.10

gives description of hydrogen-bond geometry. A perspective view of (XX) is shown

in Fig. 4.1.

Fig. 4.1 - Molecular structure of the title compound (XX) showing the atom

labeling scheme and 30% probability displacement ellipsoids. Dashed

lines indicate strong intermolecular N—H···O hydrogen bonds

between the protonated N atoms from the piperazine group in the

cinnarizinium cation and the two picrate anions. For the disordered

atoms, only major components are shown.

394

Table 4.1 - Crystal data and structure refinement

Empirical formula C38H34N8O14

Formula weight 826.73

Temperature 295(2) K

Wavelength 1.54184 Å

Crystal system Monoclinic

Space group P 21/c

Unit cell dimensions a = 15.1987(2) Å α = 90°

b =.10.09128(17) Å β = 95.9171(14)°

c = 25.0724(3) Å γ = 90°

Volume 3824.97(10) Å3

Z 4

Density (calculated) 1.436 Mg/m3

Absorption coefficient 0.949 mm-1

F(000) 1720

Crystal size 0.49 x 0.42 x 0.27 mm3

Theta range for data collection 4.82 to 73.45°.

Index ranges -18<=h<=17, -11<=k<=12, -31<=l<=20

Reflections collected 14786

Independent reflections 7319 [R(int) = 0.0237]

Completeness to theta = 67.50° 97.8 %

Absorption correction Semi-empirical from equivalents

Max. and min. transmission 1.00000 and 0.77713

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 7319 / 33 / 584

Goodness-of-fit on F2 1.026

Final R indices [I>2sigma(I)] R1 = 0.0950, wR2 = 0.2766

R indices (all data) R1 = 0.1085, wR2 = 0.2956

Extinction coefficient 0.0016(5)

Largest diff. peak and hole 1.241 and -0.554 e.Å-3

395

Table 4.2 - Atomic coordinates (x 104) and equivalent isotropic

displacement parameters (Å2x 10

3) for the non-hydrogen

Atoms x y z U(eq)

N(1) 7598(1) 8088(2) 5568(1) 34(1)

N(2) 7578(2) 5192(2) 5581(1) 41(1)

C(1) 8404(2) 7281(3) 5479(1) 41(1)

C(2) 8388(2) 5960(3) 5764(1) 43(1)

C(3) 6771(2) 5985(3) 5650(1) 43(1)

C(4) 6789(2) 7305(3) 5363(1) 40(1)

C(5) 7623(2) 9423(3) 5288(1) 38(1)

C(6) 6786(2) 10215(3) 5327(1) 39(1)

C(7) 6351(2) 10762(4) 4866(1) 52(1)

C(8) 5647(2) 11606(4) 4892(2) 67(1)

C(9) 5357(2) 11909(4) 5378(2) 62(1)

C(10) 5762(2) 11343(4) 5838(1) 58(1)

C(11) 6478(2) 10514(3) 5815(1) 50(1)

C(12) 8429(2) 10224(3) 5491(1) 42(1)

C(13) 8877(2) 10923(5) 5127(2) 67(1)

C(14) 9560(3) 11784(5) 5301(2) 87(1)

C(15) 9817(2) 11932(5) 5836(2) 81(1)

C(16) 9391(3) 11227(4) 6203(2) 68(1)

C(17) 8696(2) 10395(3) 6035(1) 52(1)

C(18A) 7558(3) 3855(3) 5861(1) 56(1)

C(19A) 7334(4) 3968(6) 6448(3) 53(1)

C(20A) 7954(4) 3925(5) 6851(2) 52(1)

C(18B) 7558(3) 3855(3) 5861(1) 56(1)

C(19B) 7857(6) 3936(8) 6445(4) 53(1)

C(20B) 7276(6) 3933(8) 6795(4) 52(1)

C(21) 7708(4) 3986(4) 7410(2) 85(2)

C(22) 8490(4) 3980(4) 7750(2) 86(1)

C(23) 8478(3) 3987(4) 8290(2) 80(1)

C(24) 7713(3) 3986(4) 8519(1) 67(1)

C(25) 6925(3) 4009(4) 8202(2) 67(1)

C(26) 6924(3) 4006(4) 7651(2) 74(1)

O(1A) 7492(2) 7961(3) 6618(1) 70(1)

O(2AA) 5796(8) 7715(15) 6489(1) 114(3)

O(3AA) 5079(6) 8050(20) 7156(4) 171(5)

O(2AB) 5630(20) 7460(40) 6503(5) 114(3)

O(3AB) 5306(15) 8620(30) 7154(12) 171(5)

O(4A) 6451(2) 7000(3) 8923(1) 87(1)

O(5A) 7845(2) 7066(3) 9078(1) 82(1)

O(6AA) 9619(2) 7912(10) 7695(2) 137(3)

O(7AA) 9176(3) 7442(11) 6890(2) 146(3)

O(6AB) 9526(17) 8530(20) 7506(14) 137(3)

O(7AB) 9250(20) 6800(40) 7040(20) 146(3)

N(1A) 5760(2) 7798(4) 6966(1) 70(1)

N(2A) 7177(2) 7113(3) 8773(1) 59(1)

N(3A) 9035(2) 7636(4) 7349(1) 76(1)

C(1A) 7411(2) 7723(3) 7095(1) 43(1)

C(2A) 6581(2) 7629(3) 7317(1) 46(1)

396

C(3A) 6492(2) 7437(3) 7857(1) 49(1)

C(4A) 7243(2) 7306(3) 8206(1) 45(1)

C(5A) 8071(2) 7370(3) 8033(1) 48(1)

C(6A) 8152(2) 7560(3) 7498(1) 47(1)

O(1B) 7061(2) 4820(4) 4569(1) 93(1)

O(2B) 5341(2) 4626(5) 4269(1) 123(2)

O(3B) 5006(3) 5434(6) 3497(2) 133(2)

O(4BA) 6724(3) 4103(8) 2107(1) 148(3)

O(5BA) 8120(3) 4152(9) 2243(1) 138(3)

O(4BB) 6765(16) 3810(70) 2110(4) 148(3)

O(5BB) 8060(20) 4600(70) 2237(5) 138(3)

O(6BA) 9440(3) 3758(7) 4116(2) 113(2)

O(6BB) 9362(8) 4720(16) 3949(3) 113(2)

O(7B) 8811(3) 4849(5) 4689(1) 125(2)

N(1B) 5530(2) 4922(4) 3829(1) 79(1)

N(2B) 7398(3) 4173(3) 2406(1) 101(2)

N(3B) 8819(2) 4394(4) 4243(1) 84(1)

C(1B) 7203(3) 4642(3) 4089(1) 63(1)

C(2B) 6467(3) 4641(3) 3699(2) 60(1)

C(3B) 6515(3) 4470(3) 3165(2) 62(1)

C(4B) 7307(3) 4302(3) 2974(1) 61(1)

C(5B) 8079(3) 4289(3) 3312(2) 66(1)

C(6B) 8022(3) 4457(4) 3859(2) 67(1)

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

Table 4.3 - Anisotropic displacement parameters (Å2x 10

3) for the

non-hydrogen atoms

Atoms U

11 U

22 U

33 U

23 U

13 U

12

N(1) 33(1) 44(1) 25(1) 0(1) 4(1) 3(1)

N(2) 50(1) 43(1) 30(1) -4(1) 5(1) 2(1)

C(1) 32(1) 48(1) 42(1) -1(1) 8(1) 5(1)

C(2) 41(1) 48(2) 40(1) 2(1) 0(1) 7(1)

C(3) 41(1) 50(2) 39(1) -4(1) 6(1) -5(1)

C(4) 36(1) 50(2) 34(1) -1(1) 0(1) 2(1)

C(5) 48(1) 45(1) 22(1) 3(1) 6(1) 4(1)

C(6) 41(1) 41(1) 35(1) 1(1) 0(1) 1(1)

C(7) 50(2) 67(2) 39(1) 10(1) -1(1) 5(1)

C(8) 55(2) 77(2) 65(2) 20(2) -9(2) 15(2)

C(9) 43(2) 62(2) 79(2) -4(2) -3(2) 13(1)

C(10) 48(2) 68(2) 60(2) -14(2) 6(1) 12(2)

C(11) 51(2) 59(2) 38(1) -3(1) 1(1) 12(1)

C(12) 40(1) 48(1) 39(1) 6(1) 10(1) 5(1)

C(13) 51(2) 98(3) 55(2) 24(2) 14(1) -2(2)

C(14) 51(2) 110(4) 101(3) 41(3) 20(2) -15(2)

C(15) 45(2) 83(3) 113(4) 19(2) -5(2) -18(2)

C(16) 63(2) 70(2) 69(2) -6(2) -5(2) -12(2)

C(17) 53(2) 62(2) 42(2) 1(1) 5(1) -9(1)

C(18A) 79(2) 42(2) 47(2) 0(1) 8(2) 2(1)

C(19A) 58(3) 48(2) 55(3) 9(2) 11(3) 1(3)

397

C(20A) 60(2) 50(2) 46(2) 5(2) 11(2) 4(2)

C(18B) 79(2) 42(2) 47(2) 0(1) 8(2) 2(1)

C(19B) 58(3) 48(2) 55(3) 9(2) 11(3) 1(3)

C(20B) 60(2) 50(2) 46(2) 5(2) 11(2) 4(2)

C(21) 167(5) 39(2) 54(2) 4(2) 38(3) 1(2)

C(22) 106(4) 59(2) 98(4) 7(2) 41(3) 3(2)

C(23) 85(3) 58(2) 93(3) 7(2) 0(2) 5(2)

C(24) 107(3) 51(2) 42(2) 0(1) 5(2) 4(2)

C(25) 84(2) 53(2) 67(2) -6(2) 19(2) 2(2)

C(26) 108(3) 47(2) 63(2) -1(2) -19(2) 3(2)

O(1A) 110(2) 77(2) 25(1) 5(1) 15(1) -5(2)

O(2AA) 96(5) 169(7) 68(2) -41(3) -37(2) 38(5)

O(3AA) 38(4) 375(16) 97(3) -34(7) -5(4) 14(6)

O(2AB) 96(5) 169(7) 68(2) -41(3) -37(2) 38(5)

O(3AB) 38(4) 375(16) 97(3) -34(7) -5(4) 14(6)

O(4A) 112(2) 101(2) 54(2) 10(1) 44(2) -5(2)

O(5A) 120(2) 95(2) 29(1) 10(1) 4(1) 2(2)

O(6AA) 63(2) 277(8) 69(3) 39(4) -6(2) -28(3)

O(7AA) 90(3) 273(9) 84(4) -58(5) 50(3) -39(4)

O(6AB) 63(2) 277(8) 69(3) 39(4) -6(2) -28(3)

O(7AB) 90(3) 273(9) 84(4) -58(5) 50(3) -39(4)

N(1A) 61(2) 90(2) 58(2) -14(2) -7(1) 0(2)

N(2A) 96(2) 50(1) 35(1) 2(1) 21(1) 1(1)

N(3A) 59(2) 115(3) 56(2) 6(2) 16(1) -7(2)

C(1A) 64(2) 38(1) 27(1) -3(1) 6(1) -3(1)

C(2A) 57(2) 45(1) 36(1) -4(1) 0(1) -2(1)

C(3A) 59(2) 45(2) 45(2) -4(1) 16(1) -8(1)

C(4A) 70(2) 38(1) 29(1) 3(1) 11(1) 0(1)

C(5A) 61(2) 49(2) 33(1) 3(1) 3(1) 2(1)

C(6A) 55(2) 53(2) 35(1) 0(1) 10(1) -5(1)

O(1B) 82(2) 147(3) 49(1) -19(2) 6(1) -6(2)

O(2B) 78(2) 168(4) 127(3) 17(3) 31(2) 7(2)

O(3B) 85(2) 170(5) 140(4) 34(3) -8(2) 32(3)

O(4BA) 317(8) 74(3) 42(2) -5(2) -35(3) 13(3)

O(5BA) 271(7) 80(5) 82(2) 6(2) 110(4) 13(3)

O(4BB) 317(8) 74(3) 42(2) -5(2) -35(3) 13(3)

O(5BB) 271(7) 80(5) 82(2) 6(2) 110(4) 13(3)

O(6BA) 63(2) 183(7) 92(3) -20(4) 7(2) 36(3)

O(6BB) 63(2) 183(7) 92(3) -20(4) 7(2) 36(3)

O(7B) 86(2) 199(5) 86(2) -44(3) -13(2) 23(3)

N(1B) 86(2) 74(2) 78(2) 8(2) 8(2) -10(2)

N(2B) 216(6) 48(2) 43(2) 4(1) 29(3) 12(2)

N(3B) 67(2) 105(3) 80(2) -16(2) 8(2) -5(2)

C(1B) 106(3) 48(2) 36(2) -7(1) 8(2) -4(2)

C(2B) 79(2) 45(2) 61(2) -2(1) 23(2) -5(2)

C(3B) 85(2) 40(2) 57(2) -3(1) -14(2) -5(2)

C(4B) 114(3) 38(1) 33(2) 1(1) 17(2) 3(2)

C(5B) 75(2) 39(2) 89(3) 2(2) 30(2) 2(2)

C(6B) 77(2) 47(2) 71(2) 1(2) -18(2) -7(2)

The anisotropic displacement factor exponent takes the form: -2π2[h

2a*

2U

11+ ... + 2 h k a* b* U

12]

398

Table 4.4 - Bond lengths [Å] for the non-hydrogen atoms

Atoms Length Atoms Length

N(1)-C(1) 1.506(3) N(1)-C(4) 1.506(3)

N(1)-C(5) 1.522(3) N(2)-C(2) 1.487(4)

N(2)-C(3) 1.490(4) N(2)-C(18A) 1.523(4)

C(1)-C(2) 1.513(4) C(3)-C(4) 1.515(4)

C(5)-C(12) 1.511(4) C(5)-C(6) 1.514(4)

C(6)-C(7) 1.386(4) C(6)-C(11) 1.388(4)

C(7)-C(8) 1.375(5) C(8)-C(9) 1.371(6)

C(9)-C(10) 1.375(5) C(10)-C(11) 1.378(4)

C(12)-C(13) 1.387(4) C(12)-C(17) 1.394(4)

C(13)-C(14) 1.390(6) C(14)-C(15) 1.365(7)

C(15)-C(16) 1.377(6) C(16)-C(17) 1.381(5)

C(18A)-C(19A) 1.549(7) C(19A)-C(20A) 1.310(9)

C(20A)-C(21) 1.488(7) C(19B)-C(20B) 1.307(13)

C(20B)-C(21) 1.613(10) C(21)-C(26) 1.390(7)

C(21)-C(22) 1.390(8) C(22)-C(23) 1.356(7)

C(23)-C(24) 1.349(7) C(24)-C(25) 1.368(6)

C(25)-C(26) 1.383(6) O(1A)-C(1A) 1.240(3)

O(2AA)-N(1A) 1.2078(16) O(3AA)-N(1A) 1.2083(17)

O(2AB)-N(1A) 1.2079(17) O(3AB)-N(1A) 1.2081(17)

O(4A)-N(2A) 1.2079(16) O(5A)-N(2A) 1.2086(16)

O(6AA)-N(3A) 1.2084(16) O(7AA)-N(3A) 1.2078(16)

O(6AB)-N(3A) 1.2080(17) O(7AB)-N(3A) 1.2080(17)

N(1A)-C(2A) 1.461(4) N(2A)-C(4A) 1.447(3)

N(3A)-C(6A) 1.433(4) C(1A)-C(2A) 1.432(4)

C(1A)-C(6A) 1.443(4) C(2A)-C(3A) 1.388(4)

C(3A)-C(4A) 1.370(5) C(4A)-C(5A) 1.375(4)

C(5A)-C(6A) 1.372(4) O(1B)-C(1B) 1.259(4)

O(2B)-N(1B) 1.2063(16) O(3B)-N(1B) 1.2073(17)

O(4BA)-N(2B) 1.2074(16) O(5BA)-N(2B) 1.2085(16)

O(4BB)-N(2B) 1.2081(17) O(5BB)-N(2B) 1.2082(17)

O(6BA)-N(3B) 1.2103(17) O(6BB)-N(3B) 1.2077(17)

O(7B)-N(3B) 1.2087(16) N(1B)-C(2B) 1.522(5)

N(2B)-C(4B) 1.452(4) N(3B)-C(6B) 1.469(4)

C(1B)-C(2B) 1.407(6) C(1B)-C(6B) 1.437(6)

C(2B)-C(3B) 1.358(5) C(3B)-C(4B) 1.352(6)

C(4B)-C(5B) 1.375(6) C(5B)-C(6B) 1.394(6)

Table 4.5 - Bond angles [º] for the non-hydrogen atoms

Atoms Angle Atoms Angle

C(1)-N(1)-C(4) 108.3(2) C(1)-N(1)-C(5) 110.61(19)

C(4)-N(1)-C(5) 111.46(19) C(2)-N(2)-C(3) 110.4(2)

C(2)-N(2)-C(18A) 112.0(2) C(3)-N(2)-C(18A) 111.5(2)

N(1)-C(1)-C(2) 110.7(2) N(2)-C(2)-C(1) 111.4(2)

N(2)-C(3)-C(4) 111.2(2) N(1)-C(4)-C(3) 110.7(2)

C(12)-C(5)-C(6) 110.7(2) C(12)-C(5)-N(1) 112.1(2)

C(6)-C(5)-N(1) 112.1(2) C(7)-C(6)-C(11) 118.3(3)

C(7)-C(6)-C(5) 119.2(2) C(11)-C(6)-C(5) 122.3(2)

399

C(8)-C(7)-C(6) 120.9(3) C(9)-C(8)-C(7) 120.3(3)

C(8)-C(9)-C(10) 119.6(3) C(9)-C(10)-C(11) 120.3(3)

C(10)-C(11)-C(6) 120.6(3) C(13)-C(12)-C(17) 117.9(3)

C(13)-C(12)-C(5) 119.1(3) C(17)-C(12)-C(5) 122.7(2)

C(12)-C(13)-C(14) 120.9(4) C(15)-C(14)-C(13) 120.4(4)

C(14)-C(15)-C(16) 119.5(4) C(15)-C(16)-C(17) 120.6(4)

C(16)-C(17)-C(12) 120.7(3) N(2)-C(18A)-C(19A) 113.0(3)

C(20A)-C(19A)-C(18A) 121.2(5) C(19A)-C(20A)-C(21) 119.6(6)

C(19B)-C(20B)-C(21) 113.9(8) C(26)-C(21)-C(22) 116.8(4)

C(26)-C(21)-C(20A) 136.0(5) C(22)-C(21)-C(20A) 107.1(5)

C(26)-C(21)-C(20B) 97.7(5) C(22)-C(21)-C(20B) 145.5(5)

C(20A)-C(21)-C(20B) 38.4(4) C(23)-C(22)-C(21) 120.9(5)

C(24)-C(23)-C(22) 121.8(5) C(23)-C(24)-C(25) 119.6(4)

C(24)-C(25)-C(26) 119.4(4) C(25)-C(26)-C(21) 121.5(4)

O(2AA)-N(1A)-O(2AB) 17(2) O(2AA)-N(1A)-O(3AB) 121(2)

O(2AB)-N(1A)-O(3AB) 122.2(2) O(2AA)-N(1A)-O(3AA) 122.2(2)

O(2AB)-N(1A)-O(3AA) 112.4(18) O(3AB)-N(1A)-O(3AA) 32.6(15)

O(2AA)-N(1A)-C(2A) 117.7(6) O(2AB)-N(1A)-C(2A) 125.8(15)

O(3AB)-N(1A)-C(2A) 109.5(12) O(3AA)-N(1A)-C(2A) 120.1(6)

O(4A)-N(2A)-O(5A) 122.20(19) O(4A)-N(2A)-C(4A) 118.5(2)

O(5A)-N(2A)-C(4A) 119.3(2) O(7AA)-N(3A)-O(7AB) 37(3)

O(7AA)-N(3A)-O(6AB) 105.5(16) O(7AB)-N(3A)-O(6AB) 122.2(2)

O(7AA)-N(3A)-O(6AA) 122.2(2) O(7AB)-N(3A)-O(6AA) 113(2)

O(6AB)-N(3A)-O(6AA) 37.9(17) O(7AA)-N(3A)-C(6A) 120.3(3)

O(7AB)-N(3A)-C(6A) 116.6(14) O(6AB)-N(3A)-C(6A) 121.2(14)

O(6AA)-N(3A)-C(6A) 117.6(3) O(1A)-C(1A)-C(2A) 124.5(3)

O(1A)-C(1A)-C(6A) 123.4(3) C(2A)-C(1A)-C(6A) 112.0(2)

C(3A)-C(2A)-C(1A) 124.5(3) C(3A)-C(2A)-N(1A) 116.1(3)

C(1A)-C(2A)-N(1A) 119.4(3) C(4A)-C(3A)-C(2A) 118.6(3)

C(4A)-C(3A)-H(3AA) 120.7 C(2A)-C(3A)-H(3AA) 120.7

C(3A)-C(4A)-C(5A) 121.6(2) C(3A)-C(4A)-N(2A) 120.1(3)

C(5A)-C(4A)-N(2A) 118.3(3) C(6A)-C(5A)-C(4A) 119.4(3)

C(6A)-C(5A)-H(5AA) 120.3 C(4A)-C(5A)-H(5AA) 120.3

C(5A)-C(6A)-N(3A) 116.3(3) C(5A)-C(6A)-C(1A) 123.9(3)

N(3A)-C(6A)-C(1A) 119.7(2) O(2B)-N(1B)-O(3B) 122.4(2)

O(2B)-N(1B)-C(2B) 117.8(3) O(3B)-N(1B)-C(2B) 119.8(3)

O(4BA)-N(2B)-O(4BB) 14(4) O(4BA)-N(2B)-O(5BB) 119.1(15)

O(4BB)-N(2B)-O(5BB) 122.1(2) O(4BA)-N(2B)-O(5BA) 122.2(2)

O(4BB)-N(2B)-O(5BA) 118.8(11) O(5BB)-N(2B)-O(5BA) 22(3)

O(4BA)-N(2B)-C(4B) 116.9(3) O(4BB)-N(2B)-C(4B) 118.5(3)

O(5BB)-N(2B)-C(4B) 118.5(3) O(5BA)-N(2B)-C(4B) 120.9(3)

O(6BB)-N(3B)-O(7B) 122.2(2) O(6BB)-N(3B)-O(6BA) 51.9(8)

O(7B)-N(3B)-O(6BA) 121.8(2) O(6BB)-N(3B)-C(6B) 99.0(7)

O(7B)-N(3B)-C(6B) 120.2(3) O(6BA)-N(3B)-C(6B) 117.5(3)

O(1B)-C(1B)-C(2B) 117.6(4) O(1B)-C(1B)-C(6B) 130.1(4)

C(2B)-C(1B)-C(6B) 112.4(3) C(3B)-C(2B)-C(1B) 124.5(4)

C(3B)-C(2B)-N(1B) 112.4(3) C(1B)-C(2B)-N(1B) 123.0(3)

C(4B)-C(3B)-C(2B) 120.3(3) C(4B)-C(3B)-H(3BA) 119.9

C(2B)-C(3B)-H(3BA) 119.9 C(3B)-C(4B)-C(5B) 121.2(3)

C(3B)-C(4B)-N(2B) 122.5(4) C(5B)-C(4B)-N(2B) 116.2(4)

C(4B)-C(5B)-C(6B) 118.0(3) C(4B)-C(5B)-H(5BA) 121.0

C(6B)-C(5B)-H(5BA) 121.0 C(5B)-C(6B)-C(1B) 123.7(3)

C(5B)-C(6B)-N(3B) 120.6(4) C(1B)-C(6B)-N(3B) 115.6(3)

400

Table 4.6 - Atomic coordinates (x104) and equivalent isotropic


3) for the hydrogen atoms

Atoms x y z U(eq)

H(1N) 7590(20) 8180(30) 5924(3) 41(8)

H(2N) 7630(30) 5000(40) 5236(5) 65(11)

H(1A) 8932 7765 5613 49

H(1B) 8422 7134 5098 49

H(2A) 8907 5452 5697 52

H(2B) 8411 6109 6148 52

H(3A) 6733 6137 6029 52

H(3B) 6251 5491 5509 52

H(4A) 6790 7155 4981 48

H(4B) 6262 7806 5419 48

H(5A) 7663 9247 4907 46

H(7A) 6538 10555 4534 63

H(8A) 5367 11974 4579 80

H(9A) 4888 12494 5395 74

H(10A) 5552 11521 6166 70

H(11A) 6757 10152 6129 60

H(13A) 8718 10815 4761 81

H(14A) 9844 12263 5052 104

H(15A) 10277 12505 5951 97

H(16A) 9572 11313 6567 82

H(17A) 8403 9944 6288 63

H(18A) 8131 3432 5858 67

H(18B) 7122 3293 5662 67

H(19A) 6747 4070 6516 64

H(20A) 8545 3855 6788 62

H(18C) 6960 3509 5814 67

H(18D) 7936 3240 5694 67

H(19B) 8457 3988 6561 64

H(20B) 6669 3903 6698 62

H(22A) 9030 3972 7605 103

H(23A) 9011 3993 8508 96

H(24A) 7722 3969 8890 80

H(25A) 6394 4027 8357 80

H(26A) 6388 4017 7436 89

H(3AA) 5936 7398 7979 59

H(5AA) 8573 7284 8276 57

H(3BA) 6000 4469 2930 75

H(5BA) 8623 4172 3179 80

H(17C) 1544 9897 5831 38

401

Table 4.7 - Bond lengths [Å] for the hydrogen atoms


N(1)-H(1N) 0.901(5) N(2)-H(2N) 0.897(5)

C(1)-H(1A) 0.9700 C(1)-H(1B) 0.9700

C(2)-H(2A) 0.9700 C(2)-H(2B) 0.9700

C(3)-H(3A) 0.9700 C(3)-H(3B) 0.9700

C(4)-H(4A) 0.9700 C(4)-H(4B) 0.9700

C(5)-H(5A) 0.9800 C(7)-H(7A) 0.9300

C(8)-H(8A) 0.9300 C(9)-H(9A) 0.9300

C(10)-H(10A) 0.9300 C(11)-H(11A) 0.9300

C(13)-H(13A) 0.9300 C(14)-H(14A) 0.9300

C(15)-H(15A) 0.9300 C(16)-H(16A) 0.9300

C(17)-H(17A) 0.9300 C(18A)-H(18A) 0.9700

C(18A)-H(18B) 0.9700 C(19A)-H(19A) 0.9300

C(20A)-H(20A) 0.9300 C(19B)-H(19B) 0.9300

C(20B)-H(20B) 0.9300 C(22)-H(22A) 0.9300

C(23)-H(23A) 0.9300 C(24)-H(24A) 0.9300

C(25)-H(25A) 0.9300 C(26)-H(26A) 0.9300

C(5A)-H(5AA) 0.9300 C(3A)-H(3AA) 0.9300

C(5B)-H(5BA) 0.9300 C(3B)-H(3BA) 0.9300

Table 4.8 - Bond angles [º] for the hydrogen atoms


C(1)-N(1)-H(1N) 107(2) C(4)-N(1)-H(1N) 107(2)

C(5)-N(1)-H(1N) 112(2) C(2)-N(2)-H(2N) 105(3)

C(3)-N(2)-H(2N) 113(3) C(18A)-N(2)-H(2N) 105(3)

N(1)-C(1)-H(1A) 109.5 C(2)-C(1)-H(1A) 109.5

N(1)-C(1)-H(1B) 109.5 C(2)-C(1)-H(1B) 109.5

H(1A)-C(1)-H(1B) 108.1 N(2)-C(2)-H(2A) 109.3

C(1)-C(2)-H(2A) 109.3 N(2)-C(2)-H(2B) 109.3

C(1)-C(2)-H(2B) 109.3 H(2A)-C(2)-H(2B) 108.0

N(2)-C(3)-H(3A) 109.4 C(4)-C(3)-H(3A) 109.4

N(2)-C(3)-H(3B) 109.4 C(4)-C(3)-H(3B) 109.4

H(3A)-C(3)-H(3B) 108.0 N(1)-C(4)-H(4A) 109.5

C(3)-C(4)-H(4A) 109.5 N(1)-C(4)-H(4B) 109.5

C(3)-C(4)-H(4B) 109.5 H(4A)-C(4)-H(4B) 108.1

C(12)-C(5)-H(5A) 107.2 C(6)-C(5)-H(5A) 107.2

N(1)-C(5)-H(5A) 107.2 C(8)-C(7)-H(7A) 119.6

C(6)-C(7)-H(7A) 119.6 C(9)-C(8)-H(8A) 119.8

C(7)-C(8)-H(8A) 119.8 C(8)-C(9)-H(9A) 120.2

C(10)-C(9)-H(9A) 120.2 C(9)-C(10)-H(10A) 119.9

C(11)-C(10)-H(10A) 119.9 C(10)-C(11)-H(11A) 119.7

C(6)-C(11)-H(11A) 119.7 C(12)-C(13)-H(13A) 119.6

C(14)-C(13)-H(13A) 119.6 C(15)-C(14)-H(14A) 119.8

C(13)-C(14)-H(14A) 119.8 C(14)-C(15)-H(15A) 120.2

C(16)-C(15)-H(15A) 120.2 C(15)-C(16)-H(16A) 119.7

C(17)-C(16)-H(16A) 119.7 C(16)-C(17)-H(17A) 119.7

402

C(12)-C(17)-H(17A) 119.7 N(2)-C(18A)-H(18A) 109.0

C(19A)-C(18A)-H(18A) 109.0 N(2)-C(18A)-H(18B) 109.0

C(19A)-C(18A)-H(18B) 109.0 H(18A)-C(18A)-H(18B) 107.8

C(20A)-C(19A)-H(19A) 119.4 C(18A)-C(19A)-H(19A)119.4

C(19A)-C(20A)-H(20A) 120.2 C(21)-C(20A)-H(20A) 120.2

C(20B)-C(19B)-H(19B) 120.0 C(19B)-C(20B)-H(20B) 123.1

C(21)-C(20B)-H(20B) 123.1 C(23)-C(22)-H(22A) 119.6

C(21)-C(22)-H(22A) 119.6 C(24)-C(23)-H(23A) 119.1

C(22)-C(23)-H(23A) 119.1 C(25)-C(26)-H(26A) 119.2

C(21)-C(26)-H(26A) 119.2 C(24)-C(25)-H(25A) 120.3

C(26)-C(25)-H(25A) 120.3 C(23)-C(24)-H(24A) 120.2

C(25)-C(24)-H(24A) 120.2

Table 4.9 - Torsion angles [º]


C(4)-N(1)-C(1)-C(2) -58.5(3) C(5)-N(1)-C(1)-C(2) 179.1(2)

C(3)-N(2)-C(2)-C(1) -55.6(3) C(18A)-N(2)-C(2)-C(1) 179.5(2)

N(1)-C(1)-C(2)-N(2) 58.0(3) C(2)-N(2)-C(3)-C(4) 55.7(3)

C(18A)-N(2)-C(3)-C(4) -179.1(2) C(1)-N(1)-C(4)-C(3) 58.7(3)

C(5)-N(1)-C(4)-C(3) -179.4(2) N(2)-C(3)-C(4)-N(1) -58.2(3)

C(1)-N(1)-C(5)-C(12) -59.8(3) C(4)-N(1)-C(5)-C(12) 179.7(2)

C(1)-N(1)-C(5)-C(6) 175.0(2) C(4)-N(1)-C(5)-C(6) 54.5(3)

C(12)-C(5)-C(6)-C(7) 103.9(3) N(1)-C(5)-C(6)-C(7) -130.2(3)

C(12)-C(5)-C(6)-C(11) -70.3(3) N(1)-C(5)-C(6)-C(11) 55.7(3)

C(11)-C(6)-C(7)-C(8) 1.7(5) C(5)-C(6)-C(7)-C(8) -172.7(3)

C(6)-C(7)-C(8)-C(9) -0.8(6) C(7)-C(8)-C(9)-C(10) -1.3(6)

C(8)-C(9)-C(10)-C(11) 2.4(6) C(9)-C(10)-C(11)-C(6) -1.5(5)

C(7)-C(6)-C(11)-C(10) -0.5(5) C(5)-C(6)-C(11)-C(10) 173.7(3)

C(6)-C(5)-C(12)-C(13) -95.3(3) N(1)-C(5)-C(12)-C(13) 138.7(3)

C(6)-C(5)-C(12)-C(17) 78.5(3) N(1)-C(5)-C(12)-C(17) -47.5(4)

C(17)-C(12)-C(13)-C(14) -1.1(6) C(5)-C(12)-C(13)-C(14) 172.9(4)

C(12)-C(13)-C(14)-C(15) 1.6(7) C(13)-C(14)-C(15)-C(16) -0.4(7)

C(14)-C(15)-C(16)-C(17) -1.3(7) C(15)-C(16)-C(17)-C(12) 1.8(6)

C(13)-C(12)-C(17)-C(16) -0.6(5) C(5)-C(12)-C(17)-C(16) -174.3(3)

C(2)-N(2)-C(18A)-C(19A) 74.9(4) C(3)-N(2)-C(18A)-C(19A) -49.4(4)

N(2)-C(18A)-C(19A)-C(20A) -100.0(5) C(18A)-C(19A)-C(20A)-C(21) -177.7(4)

C(19A)-C(20A)-C(21)-C(26) 4.9(8) C(19A)-C(20A)-C(21)-C(22) -177.4(5)

C(19A)-C(20A)-C(21)-C(20B) 3.6(6) C(19B)-C(20B)-C(21)-C(26) 178.4(6)

C(19B)-C(20B)-C(21)-C(22) -4.2(12) C(19B)-C(20B)-C(21)-C(20A) -2.4(6)

C(26)-C(21)-C(22)-C(23) 0.3(6) C(20A)-C(21)-C(22)-C(23) -177.9(4)

C(20B)-C(21)-C(22)-C(23) -176.8(6) C(21)-C(22)-C(23)-C(24) 0.7(7)

C(22)-C(23)-C(24)-C(25) -1.5(6) C(23)-C(24)-C(25)-C(26) 1.3(6)

C(24)-C(25)-C(26)-C(21) -0.3(6) C(22)-C(21)-C(26)-C(25) -0.5(6)

C(20A)-C(21)-C(26)-C(25) 177.0(4) C(20B)-C(21)-C(26)-C(25) 177.8(4)

O(1A)-C(1A)-C(2A)-C(3A) -176.2(3) C(6A)-C(1A)-C(2A)-C(3A) 1.4(4)

O(1A)-C(1A)-C(2A)-N(1A) 1.2(5) C(6A)-C(1A)-C(2A)-N(1A) 178.8(3)

O(2AA)-N(1A)-C(2A)-C(3A) -166.2(9) O(2AB)-N(1A)-C(2A)-C(3A) -148(3)

O(3AB)-N(1A)-C(2A)-C(3A) 50(2) O(3AA)-N(1A)-C(2A)-C(3A) 15.6(15)

O(2AA)-N(1A)-C(2A)-C(1A) 16.2(10) O(2AB)-N(1A)-C(2A)-C(1A) 34(3)

403

O(3AB)-N(1A)-C(2A)-C(1A) -128(2) O(3AA)-N(1A)-C(2A)-C(1A) -161.9(14)

C(1A)-C(2A)-C(3A)-C(4A) -1.0(5) N(1A)-C(2A)-C(3A)-C(4A) -178.4(3)

C(2A)-C(3A)-C(4A)-C(5A) 0.4(4) C(2A)-C(3A)-C(4A)-N(2A) 179.6(3)

O(4A)-N(2A)-C(4A)-C(3A) 3.9(4) O(5A)-N(2A)-C(4A)-C(3A) -176.3(3)

O(4A)-N(2A)-C(4A)-C(5A) -176.9(3) O(5A)-N(2A)-C(4A)-C(5A) 2.9(4)


C(4A)-C(5A)-C(6A)-N(3A) 179.1(3) C(4A)-C(5A)-C(6A)-C(1A) 1.0(5)

O(7AA)-N(3A)-C(6A)-C(5A) 159.9(7) O(7AB)-N(3A)-C(6A)-C(5A) 118(4)

O(6AB)-N(3A)-C(6A)-C(5A) -64(2) O(6AA)-N(3A)-C(6A)-C(5A) -21.0(7)

O(7AA)-N(3A)-C(6A)-C(1A) -21.9(8) O(7AB)-N(3A)-C(6A)-C(1A) -63(4)

O(6AB)-N(3A)-C(6A)-C(1A) 114(2) O(6AA)-N(3A)-C(6A)-C(1A) 157.2(6)

O(1A)-C(1A)-C(6A)-C(5A) 176.2(3) C(2A)-C(1A)-C(6A)-C(5A) -1.4(4)

O(1A)-C(1A)-C(6A)-N(3A) -1.8(5) C(2A)-C(1A)-C(6A)-N(3A) -179.5(3)

O(1B)-C(1B)-C(2B)-C(3B) 179.6(4) C(6B)-C(1B)-C(2B)-C(3B) 0.7(5)

O(1B)-C(1B)-C(2B)-N(1B) 3.7(5) C(6B)-C(1B)-C(2B)-N(1B) -175.2(3)

O(2B)-N(1B)-C(2B)-C(3B) 153.8(4) O(3B)-N(1B)-C(2B)-C(3B) -26.6(6)

O(2B)-N(1B)-C(2B)-C(1B) -29.9(6) O(3B)-N(1B)-C(2B)-C(1B) 149.7(5)

C(1B)-C(2B)-C(3B)-C(4B) -0.8(5) N(1B)-C(2B)-C(3B)-C(4B) 175.5(3)

C(2B)-C(3B)-C(4B)-C(5B) 0.5(5) C(2B)-C(3B)-C(4B)-N(2B) -177.2(3)

O(4BA)-N(2B)-C(4B)-C(3B) -6.5(6) O(4BB)-N(2B)-C(4B)-C(3B) -23(4)

O(5BB)-N(2B)-C(4B)-C(3B) 147(4) O(5BA)-N(2B)-C(4B)-C(3B) 172.8(6)

O(4BA)-N(2B)-C(4B)-C(5B) 175.7(5) O(4BB)-N(2B)-C(4B)-C(5B) 160(4)

O(5BB)-N(2B)-C(4B)-C(5B) -31(4) O(5BA)-N(2B)-C(4B)-C(5B) -5.0(7)

C(3B)-C(4B)-C(5B)-C(6B) -0.1(5) N(2B)-C(4B)-C(5B)-C(6B) 177.8(3)

C(4B)-C(5B)-C(6B)-C(1B) 0.0(5) C(4B)-C(5B)-C(6B)-N(3B) 177.2(3)

O(1B)-C(1B)-C(6B)-C(5B) -179.0(4) C(2B)-C(1B)-C(6B)-C(5B) -0.3(5)


O(6BB)-N(3B)-C(6B)-C(5B) 26.1(7) O(7B)-N(3B)-C(6B)-C(5B) 161.9(5)

O(6BA)-N(3B)-C(6B)-C(5B) -25.5(7) O(6BB)-N(3B)-C(6B)-C(1B) -156.5(8)

O(7B)-N(3B)-C(6B)-C(1B) -20.7(6) O(6BA)-N(3B)-C(6B)-C(1B) 151.9(5)

Cg5 and Cg6 are the centroids of the C6–C11 and C12–C17 rings, respectively.

Table 4.10 – Hydrogen-bond geometry [Å and º]

D—H…A D—H H···A D···A D—H···A

N1—H1N…O1A 0.90 (1) 1.77 (1) 2.658 (3) 168 (3)

N2—H2N…O1B 0.90 (1) 1.83 (3) 2.603 (3) 143 (4)

N2—H2N…O7BA 0.90 (1) 2.30 (3) 3.047 (5) 140 (3)

C3—H3A…O2AA 0.97 2.50 3.214 (8) 130

C3—H3A…O2AB 0.97 2.52 3.242 (17) 131

C2—H2B…O7AA 0.97 2.48 3.304 (5) 142

C2—H2B…O7AB 0.97 2.54 3.42 (4) 151

C11—H11A…O4BAi 0.93 2.57 3.244 (4) 130

C17—H17A…O1A 0.93 2.62 3.473 (4) 154

C17—H17A…O5BBi 0.93 2.52 3.267 (8) 138

C18A—H18A…Cg6ii 0.97 2.88 3.742 (5) 148

C18A—H18B…Cg5ii 0.97 2.83 3.762 (1) 161

C18A—H18C…Cg5ii 0.97 3.00 3.762 (1) 137

C18A—H18D…Cg6ii 0.97 2.84 3.742 (5) 155

Symmetry codes: (i) x;y + 3/2; z + 1/2; (ii) x; y +1; z.

404

Table 4.11 - Cg···Cg π stacking interactions

Cg4, Cg5, Cg6 are the centroids of rings C21–C26. C1A–C6A, C1B–C6B.

CgX···CgY (Å) CgX···Perp (Å) CgY···Perp (Å)

Cg4···Cg5i 3.658 (2) -3.3929 (16) 3.5387 (12)

Cg4···Cg6ii 3.834 (2) -3.2298 (17) -3.4992 (13)

Cg5···Cg6iii 3.7302 (18) 3.2823 (12) 3.3358 (13)

[Symmetry codes: (i) x, y, z; x, 1/2-y, 1/2+z; x, 3/2-y, 1/2+z]

Fig. 4.2 – Hydrogen bonding interactions in the title compound

Fig. 4.3 – Packing of the molecules along a axis

405

Fig. 4.4 – Packing of the molecules along b axis

Fig. 4.5 – Packing of the molecules along c axis

406

Fig. 4.6 - Packing diagram of the title compound viewed down the a axis.

Dashed lines indicate N—H···O hydrogen bonds and weak C—H···O

intermolecular interactions creating a 2-D network structure.

Displacement ellipsoids are drawn at the 30% probability level in Fig. 4.1.

Dashed lines indicate strong intermolecular N—H···O hydrogen bonds between the

protonated N atoms from the piperazine group in the cinnarizinium cation and the two

picrate anions. For the disordered atoms, only major components are shown. Fig. 4.2.

Hydrogen bonding interactions in the title compound is shown in Fig. 4.2. Packing of

the molecules along a, b and c axes are shown in figures 4.3, 4.4 and 4.5 respectively,

with the hydrogen bonding interactions shown in dashed lines. Packing diagram of the

title compound viewed down the a axis is shown in Fig. 4.6. Dashed lines indicate

N—H···O hydrogen bonds and weak C—H···O intermolecular interactions creating a

2-D network structure.

In the cinnarizinium dication of the title compound, (XX), [systematic name:

1-benzhydryl-4-cinnamyl-piperazine dipicrate] the piperazine group is protonated at

both N atoms and adopts a slightly distorted chair conformation with puckering

parameters Q, θ and φ of 0.58 (3) Å, 177.1 (0)° and 175.518 (5)° (Cremer & Pople,

1975) (Fig. 4.1). For an ideal chair θ has a value of 0 or 180°. The dihedral angle

between the mean planes of the cation piperazine ring and three benzene rings or the

407

six-membered rings of the picrate anions are 75.9 (6)° 80.0 (2)°, 80.4 (9)° or 71.4 (9)°

and 86.7 (6)°, respectively. Bond distances (Allen et al., 1987) and angles are in

normal ranges. Strong N—H···Ohydroxy cation-anion hydrogen bonds link the dication

and two anions. In the cation, the (2E)-3-phenylprop-2-ene-1yl fragment is disordered

over two positions in a ratio of 0.586 (4): 0.414 (4). Two nitro groups in one anion

(A) and three in the other (B) demonstrate rotational disorder [O2AA & O3AA (0.68

(2)), O2AB & O3AB (0.32 (2)); O6AA & O7AA (0.851 (14)), O6AB & O7AB

(0.149 (14)); O2BA & O3BA (0.80 (2)), O2BB & O3BB (0.20 (2)); O4BA & O5BB

(0.951 (19)), O4BB & O5BB (0.050 (19)); O6BA & O7BA (0.756 (8)), O6BB &

O7BB (0.244 (8))]. The crystal packing is stabilized by π–π (Table 4.10), C—H···π-

ring and C—H···O (Table 4.10) weak intermolecular interactions creating a 2-D

network structure (Fig. 4.6).

* * * * *

408

Section 4.3

Crystal structure studies of enrofloxacinium picrate

Abstract

There is one cation–anion pair in the asymmetric unit of the title compound

[systematic name: 4-(3-carboxy-6-fluoro-4-oxo-1,4-dihydroquinolin-7-yl)-1-ethylpiperazin

-1-ium 2,4,6-trinitrophenolate], C19H23FN3O3+

∙C6H2N3O7-. The six-membered piperazine

group in the cation adopts a slightly distorted chair conformation and contains a

protonated N atom. The dihedral angles between the mean planes of the cyclopropyl

and piperazine rings in the cation with the 10-atom ring system of the quinolone

group are 48.1 (1) and 69.9 (5)°, respectively. The picrate anion interacts with

theprotonated N atom of an adjacent cation through a bifurcated N—H···O three-

center hydrogen bond, forming an R12(6) ring motif. Furthermore, there is an

intramolecular O—H···O hydrogen bond. The dihedral angle between the mean planes

of the anion benzene and cation piperizine, quinoline and cyclopropyl rings are 61.3

(6), 31.1 (4) and 70.4 (9)°, respectively.

The mean planes of the two o-NO2 and single p-NO2 groups in the picrate

anion are twisted by 6.7 (6), 38.3 (9) and 12.8 (7)° with respect to the mean plane of

the benzene ring. Strong N—H···O and weak intermolecular C—H···O hydrogen

bonds in concert with weak π–π stacking interactions [centroid–centroid distances =

3.5785 (13), 3.7451 (12) and 3.6587 (13) Å] dominate the crystal packing. No

classical hydrogen bonds found for the present structure.

The title compound, crystallizes in a triclinic space group P ī with a = 7.211

Å; b = 12.577 Å; c = 16.236 Å; α = 105.56 °; β = 96.37°; γ = 96.22°; V = 1395.0 Å3;

Z = 2; Dcal = 1.399 Mg/m3 at T = 295(2) K. The structure was solved by direct

methods and refined by full-matrix least-squares procedures to final R1 = 0.0567 and

wR2 = 0.1626 using 5443 reflections.

409

Introduction

Enrofloxacin is a fluoroquinolone antibiotic and is a synthetic chemotherapeutic

agent from the class of the fluoroquinolone carboxylic acid derivatives. It has

antibacterial activity against a broad spectrum of Gram-negative and Gram-positive

bacteria. Its mechanism of action is not thoroughly understood, but it is believed to act

by inhibiting bacterial DNA gyrase (a type-II topoisomerase), thereby preventing

DNA supercoiling and DNA synthesis. The chemical and biological aspects of

fluoroquinolones is described (Bhanot et al., 2001; Scholar, 2003). The crystal

structure of norfloxacin hydrochloride (Zou et al., 2005) and norfloxacin methanol

solvate (Wang et al., 2005) have already been reported. The crystal structure of a

copper complex of enrofloxacin (Recillas-Mota et al., 2007), norfloxacin picrate (Hu

& Yu, 2005) and 2-hydroxyethanaminium enrofloxacinate (Sun et al., 2004) are

reported. Recently, the crystal structures of propiverine picrate (Jasinski et al., 2010),

imatinibium dipicrate (Jasinski et al., 2010a) and chlorimipraminium picrate (Jasinski

et al., 2010b) have been reported. In continuation of our work on picrates of

biologically active compounds, the present section reports the crystal structure of

(XXI), C25H24FN6O10, obtained by the interaction of picric acid and enrofloxacin.

(XXI)


Experimental

Enrofloxacin (3.59 g, 0.1mol) and picric acid (2.99 g, 0.1 mol) were dissolved

in mixture of acetonitrile and dimethyl sulfoxide (80:20 v/v). The solution was stirred

for 15 min over a heating magnetic stirrer at 333 K. The resulting solution was kept

aside at room temperature. After few days, X-ray quality crystals of the title

compound were grown by slow evaporation (m.p : 490 – 493 K).

410


N N

O

HO

O

N

NO2

O2N NO2

O

CH3

H

F

N

F

O

N

N

O

HO

CH3

OH

NO2O2N

NO2

+

CH3CN + DMSO

Reaction scheme

Refinement

All H atoms were refined using the riding model with Atom—H lengths of

0.93 & 0.98Å (CH), 0.97Å (CH2), 0.96Å (CH3), 0.91Å (NH) or 0.82 (OH). Isotropic

displacement parameters for these atoms were set to 1.20 times (NH), 1.19–1.20 (CH,

CH2) or 1.49 (CH3, OH) times Ueq of the parent atom.

Special details









set to zero for negative F. The threshold expression of F2 > σ (F

2) is used only for

411

calculating Rfactors(gt) etc. and is not relevant to the choice of reflections for



Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINTPlus (Bruker,

1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97

(Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997);

molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for

publication: SHELXTL.






are given in Tables 4.15 and 4.16 respectively. Table 4.17 lists atomic coordinates of

the hydrogen atoms. The bond lengths and bond angles involving the hydrogen atoms

are listed in Tables 4.18 and 4.19. The torsion angles are presented in Table 4.20.

Hydrogen-bonding geometry is shown in Table 4.21. Table 4.22 gives Cg···Cgπ

stacking interactions. A perspective view of (XXI), is shown in Fig. 4.7 with

displacement ellipsoids are drawn at the 50% probability level.

Fig. 4.7 - Molecular structure of the title compound showing the atom labeling

scheme and 50% probability displacement ellipsoids. Dashed lines

indicate a bifurcated N—H···O intermolecular, three-centered hydrogen

bond formed between the protonated N atom from the enrofloxacin

cation and the picrate anion providing a R12(6) ring motif.

412


Empirical formula C25H24FN6O10




Crystal system Triclinic

Space group P ī

Unit cell dimensions a = 7.211 Å α = 105.56°

b = 12.577 Å β = 96.37°

c = 16.236 Å γ = 96.22°

Volume 1395.0 Å3

Z 2



F(000) 610



Index ranges -5<=h<=8, -15<=k<=14, -20<=l<=20












413



3) for the non-hydrogen atoms

Atoms x y z U(eq)

F(1) 391(3) 1439(1) 290(1) 78(1)

O(1) 4038(4) 7253(2) -1009(2) 92(1)

O(2) 3075(3) 5635(2) -1993(1) 75(1)

O(3) 2076(3) 3934(2) -1521(1) 61(1)

N(1) 2700(3) 5942(2) 971(1) 45(1)

N(2) 978(3) 2723(2) 2012(2) 58(1)

N(3) 4000(3) 2675(2) 3331(2) 59(1)

C(1) 1315(3) 3205(2) 1353(2) 49(1)

C(2) 1817(3) 4345(2) 1490(2) 46(1)

C(3) 2153(3) 4794(2) 810(1) 40(1)

C(4) 3061(3) 6357(2) 320(2) 46(1)

C(5) 2939(3) 5724(2) -523(2) 47(1)

C(6) 3402(4) 6291(3) -1183(2) 62(1)

C(7) 2320(3) 4552(2) -743(2) 46(1)

C(8) 1949(3) 4099(2) -38(1) 44(1)

C(9) 1367(3) 2958(2) -189(2) 51(1)

C(10) 1050(4) 2542(2) 476(2) 55(1)

C(11) 2677(4) 6701(2) 1821(2) 52(1)

C(12) 4141(4) 6776(3) 2564(2) 64(1)

C(13) 4141(5) 7694(3) 2159(2) 74(1)

C(14) 1711(5) 1683(3) 2041(2) 69(1)

C(15) 3729(4) 1898(3) 2446(2) 64(1)

C(16) 3177(5) 3720(2) 3332(2) 65(1)

C(17) 1145(4) 3435(3) 2885(2) 61(1)

C(18) 6052(5) 2905(4) 3705(3) 92(1)

C(19) 6392(7) 3391(5) 4650(3) 129(2)

O(1A) 1748(3) 2238(2) 4477(1) 79(1)

O(2A) 1953(6) 4176(2) 5793(3) 138(2)

O(3A) -251(4) 3841(2) 6488(2) 93(1)

O(4A) 867(4) 906(2) 7833(2) 94(1)

O(5A) 2089(4) -501(2) 7156(2) 92(1)

O(6A) 3080(3) -914(2) 4274(1) 76(1)

O(7A) 3470(4) 487(2) 3776(2) 94(1)

N(1A) 996(4) 3559(2) 6075(2) 73(1)

N(2A) 1541(4) 400(2) 7216(2) 64(1)

N(3A) 2990(3) 67(2) 4326(1) 59(1)

C(1A) 1856(3) 1834(2) 5099(2) 53(1)

C(2A) 1377(4) 2406(2) 5932(2) 53(1)

C(3A) 1248(4) 1958(2) 6595(2) 52(1)

C(4A) 1674(3) 878(2) 6506(2) 49(1)

C(5A) 2255(3) 292(2) 5764(2) 49(1)

C(6A) 2362(3) 748(2) 5089(2) 49(1)


414


3)

for the non-hydrogen atoms

Atoms U

11 U

22 U

33 U

23 U

13 U

12

F(1) 108(1) 58(1) 63(1) 18(1) 3(1) -3(1)

O(1) 128(2) 80(2) 78(2) 41(1) 32(1) -1(2)

O(2) 84(1) 108(2) 44(1) 32(1) 22(1) 22(1)

O(3) 70(1) 76(1) 35(1) 9(1) 12(1) 12(1)

N(1) 44(1) 56(1) 37(1) 13(1) 8(1) 12(1)

N(2) 64(1) 66(1) 53(1) 29(1) 11(1) 12(1)

N(3) 63(1) 71(2) 54(1) 36(1) 12(1) 13(1)

C(1) 48(1) 59(2) 46(1) 22(1) 9(1) 11(1)

C(2) 48(1) 56(1) 36(1) 13(1) 5(1) 15(1)

C(3) 37(1) 52(1) 34(1) 13(1) 6(1) 14(1)

C(4) 43(1) 56(1) 45(1) 18(1) 10(1) 11(1)

C(5) 44(1) 63(2) 40(1) 20(1) 10(1) 15(1)

C(6) 62(2) 84(2) 53(2) 33(1) 22(1) 22(2)

C(7) 37(1) 66(2) 39(1) 15(1) 8(1) 16(1)

C(8) 40(1) 58(1) 38(1) 15(1) 6(1) 16(1)

C(9) 55(1) 55(1) 41(1) 8(1) 5(1) 15(1)

C(10) 58(2) 55(2) 51(1) 15(1) 4(1) 7(1)

C(11) 52(1) 59(2) 44(1) 9(1) 11(1) 15(1)

C(12) 59(2) 80(2) 46(1) 5(1) 4(1) 12(1)

C(13) 88(2) 68(2) 56(2) 5(1) 17(2) -5(2)

C(14) 94(2) 61(2) 60(2) 30(1) 11(2) 9(2)

C(15) 85(2) 67(2) 58(2) 33(1) 30(1) 32(2)

C(16) 92(2) 61(2) 48(2) 21(1) 13(1) 19(2)

C(17) 72(2) 76(2) 54(2) 35(1) 27(1) 29(1)

C(18) 73(2) 114(3) 100(3) 55(2) 0(2) 14(2)

C(19) 123(4) 145(4) 106(4) 45(3) -42(3) -7(3)

O(1A) 99(2) 107(2) 58(1) 50(1) 29(1) 44(1)

O(2A) 217(4) 73(2) 160(3) 61(2) 100(3) 34(2)

O(3A) 114(2) 86(2) 89(2) 21(1) 33(2) 48(2)

O(4A) 158(2) 82(2) 57(1) 30(1) 48(2) 20(2)

O(5A) 136(2) 83(2) 82(2) 49(1) 40(2) 37(2)

O(6A) 93(2) 68(1) 66(1) 11(1) 23(1) 19(1)

O(7A) 143(2) 99(2) 63(1) 36(1) 57(2) 42(2)

N(1A) 97(2) 66(2) 62(2) 25(1) 16(1) 24(1)

N(2A) 87(2) 62(2) 48(1) 22(1) 19(1) 5(1)

N(3A) 62(1) 69(2) 47(1) 14(1) 11(1) 14(1)

C(1A) 51(1) 68(2) 46(1) 25(1) 10(1) 13(1)

C(2A) 55(1) 58(2) 50(1) 21(1) 11(1) 11(1)

C(3A) 56(1) 60(2) 41(1) 13(1) 10(1) 5(1)

C(4A) 54(1) 54(1) 41(1) 18(1) 10(1) 2(1)

C(5A) 49(1) 48(1) 49(1) 15(1) 7(1) 4(1)

C(6A) 47(1) 62(2) 36(1) 13(1) 7(1) 6(1)


2a*

2U

11 + ... + 2 h k a* b* U

12]

415



F(1)-C(10) 1.358(3) O(1)-C(6) 1.193(4)

O(2)-C(6) 1.331(4) O(3)-C(7) 1.274(3)

N(1)-C(4) 1.336(3) N(1)-C(3) 1.399(3)

N(1)-C(11) 1.457(3) N(2)-C(1) 1.394(3)

N(2)-C(17) 1.443(4) N(2)-C(14) 1.473(4)

N(3)-C(15) 1.484(4) N(3)-C(16) 1.499(4)

N(3)-C(18) 1.502(4) C(1)-C(2) 1.390(4)

C(1)-C(10) 1.425(4) C(2)-C(3) 1.400(3)

C(3)-C(8) 1.402(3) C(4)-C(5) 1.374(3)

C(5)-C(7) 1.427(4) C(5)-C(6) 1.486(4)

C(7)-C(8) 1.445(3) C(8)-C(9) 1.398(4)

C(9)-C(10) 1.349(4) C(11)-C(13) 1.481(4)

C(11)-C(12) 1.487(4) C(12)-C(13) 1.475(5)

C(14)-C(15) 1.493(5) C(16)-C(17) 1.521(4)

C(18)-C(19) 1.472(6) O(1A)-C(1A) 1.245(3)

O(2A)-N(1A) 1.197(4) O(3A)-N(1A) 1.208(3)

O(4A)-N(2A) 1.216(3) O(5A)-N(2A) 1.223(3)

O(6A)-N(3A) 1.223(3) O(7A)-N(3A) 1.216(3)

N(1A)-C(2A) 1.467(4) N(2A)-C(4A) 1.443(3)

N(3A)-C(6A) 1.453(3) C(1A)-C(6A) 1.448(4)

C(1A)-C(2A) 1.450(4) C(2A)-C(3A) 1.349(3)

C(3A)-C(4A) 1.399(4 C(4A)-C(5A) 1.369(3)

C(5A)-C(6A) 1.373(3)



C(4)-N(1)-C(3) 119.8(2) C(4)-N(1)-C(11) 119.4(2)

C(3)-N(1)-C(11) 120.43(19) C(1)-N(2)-C(17) 118.9(2)

C(1)-N(2)-C(14) 120.3(2) C(17)-N(2)-C(14) 108.4(2)

C(15)-N(3)-C(16) 110.9(2) C(15)-N(3)-C(18) 110.0(3)

C(16)-N(3)-C(18) 112.5(3) C(2)-C(1)-N(2) 123.5(2)

C(2)-C(1)-C(10) 115.7(2) N(2)-C(1)-C(10) 120.7(2)

C(1)-C(2)-C(3) 121.7(2) N(1)-C(3)-C(2) 120.4(2)

N(1)-C(3)-C(8) 119.3(2) C(2)-C(3)-C(8) 120.3(2)

N(1)-C(4)-C(5) 124.1(2) C(4)-C(5)-C(7) 119.4(2)

C(4)-C(5)-C(6) 118.6(2) C(7)-C(5)-C(6) 122.0(2)

O(1)-C(6)-O(2) 122.0(3) O(1)-C(6)-C(5) 123.3(3)

O(2)-C(6)-C(5) 114.7(3) O(3)-C(7)-C(5) 122.1(2)

O(3)-C(7)-C(8) 121.3(2) C(5)-C(7)-C(8) 116.6(2)

C(9)-C(8)-C(3) 118.5(2) C(9)-C(8)-C(7) 120.7(2)

C(3)-C(8)-C(7) 120.8(2) C(10)-C(9)-C(8) 120.2(2)

C(9)-C(10)-F(1) 117.9(2) C(9)-C(10)-C(1) 123.5(3)

F(1)-C(10)-C(1) 118.6(2) N(1)-C(11)-C(13) 119.5(2)

416

N(1)-C(11)-C(12) 121.3(2) C(13)-C(11)-C(12) 59.6(2)

C(13)-C(12)-C(11) 60.0(2) C(12)-C(13)-C(11) 60.41(19)

N(2)-C(14)-C(15) 111.8(2) N(3)-C(15)-C(14) 111.4(2)

N(3)-C(16)-C(17) 110.3(2) N(2)-C(17)-C(16) 112.2(2)

C(19)-C(18)-N(3) 113.4(4) O(2A)-N(1A)-O(3A) 123.3(3)

O(2A)-N(1A)-C(2A) 118.7(3) O(3A)-N(1A)-C(2A) 117.9(3)

O(4A)-N(2A)-O(5A) 123.7(2) O(4A)-N(2A)-C(4A) 118.3(2)

O(5A)-N(2A)-C(4A) 118.1(2) O(7A)-N(3A)-O(6A) 121.8(2)

O(7A)-N(3A)-C(6A) 119.8(2) O(6A)-N(3A)-C(6A) 118.3(2)

O(1A)-C(1A)-C(6A) 126.2(2) O(1A)-C(1A)-C(2A) 122.3(3)

C(6A)-C(1A)-C(2A) 111.4(2) C(3A)-C(2A)-C(1A) 125.0(3)

C(3A)-C(2A)-N(1A) 116.8(2) C(1A)-C(2A)-N(1A) 118.2(2)

C(2A)-C(3A)-C(4A) 119.2(2) C(5A)-C(4A)-C(3A) 120.5(2)

C(5A)-C(4A)-N(2A) 120.3(2) C(3A)-C(4A)-N(2A) 119.2(2)

C(4A)-C(5A)-C(6A) 120.0(2) C(5A)-C(6A)-C(1A) 123.7(2)

C(5A)-C(6A)-N(3A) 116.3(2) C(1A)-C(6A)-N(3A) 120.0(2)

Table 4.17 - Atomic coordinates ( x 104) and equivalent

isotropic displacement parameters (Å2x10


Atoms x y z U(eq)

H(3A) 3368 2331 3666 71

H(2A) 1933 4820 2047 55

H(4A) 3417 7123 445 56

H(9A) 1198 2484 -748 61

H(11A) 1420 6815 1971 62

H(12A) 3756 6902 3132 77

H(12B) 5120 6304 2462 77

H(13A) 5122 7787 1810 88

H(13B) 3758 8384 2479 88

H(14A) 1591 1193 1458 83

H(14B) 960 1308 2369 83

H(15A) 4145 1198 2471 77

H(15B) 4496 2214 2091 77

H(16A) 3917 4149 3036 78

H(16B) 3222 4173 3923 78

H(17A) 392 3063 3213 73

H(17B) 650 4119 2874 73

H(18A) 6583 2214 3561 110

H(18B) 6704 3413 3441 110

H(19A) 7711 3662 4835 194

H(19B) 6011 2830 4923 194

H(19C) 5678 3997 4808 194

H(3AA) 882 2363 7104 63

H(5AA) 2577 -416 5717 58

417



N(3)-H(3A) 0.9100 C(2)-H(2A) 0.9300

C(4)-H(4A) 0.9300 C(9)-H(9A) 0.9300

C(11)-H(11A) 0.9800 C(12)-H(12A) 0.9700

C(12)-H(12B) 0.9700 C(13)-H(13A) 0.9700

C(13)-H(13B) 0.9700 C(14)-H(14A) 0.9700

C(14)-H(14B) 0.9700 C(15)-H(15A) 0.9700

C(15)-H(15B) 0.9700 C(16)-H(16A) 0.9700

C(16)-H(16B) 0.9700 C(17)-H(17A) 0.9700

C(17)-H(17B) 0.9700 C(18)-H(18A) 0.9700

C(18)-H(18B) 0.9700 C(19)-H(19A) 0.9600

C(19)-H(19B) 0.9600 C(19)-H(19C) 0.9600

C(5A)-H(5AA) 0.9300 C(3A)-H(3AA) 0.9300



C(15)-N(3)-H(3A) 107.8 C(16)-N(3)-H(3A) 107.8

C(18)-N(3)-H(3A) 107.8 C(1)-C(2)-H(2A) 119.1

C(3)-C(2)-H(2A) 119.1 N(1)-C(4)-H(4A) 118.0

C(5)-C(4)-H(4A) 118.0 C(10)-C(9)-H(9A) 119.9

C(8)-C(9)-H(9A) 119.9 N(1)-C(11)-H(11A) 115.1

C(13)-C(11)-H(11A) 115.1 C(12)-C(11)-H(11A) 115.1

C(13)-C(12)-H(12A) 117.8 C(11)-C(12)-H(12A) 117.8

C(13)-C(12)-H(12B) 117.8 C(11)-C(12)-H(12B) 117.8

H(12A)-C(12)-H(12B) 114.9 C(12)-C(13)-H(13A) 117.7

C(11)-C(13)-H(13A) 117.7 C(12)-C(13)-H(13B) 117.7

C(11)-C(13)-H(13B) 117.7 H(13A)-C(13)-H(13B) 114.9

N(2)-C(14)-H(14A) 109.2 C(15)-C(14)-H(14A) 109.2

N(2)-C(14)-H(14B) 109.2 C(15)-C(14)-H(14B) 109.2

H(14A)-C(14)-H(14B) 107.9 N(3)-C(15)-H(15A) 109.3

C(14)-C(15)-H(15A) 109.3 N(3)-C(15)-H(15B) 109.3

C(14)-C(15)-H(15B) 109.3 H(15A)-C(15)-H(15B) 108.0

N(3)-C(16)-H(16A) 109.6 C(17)-C(16)-H(16A) 109.6

N(3)-C(16)-H(16B) 109.6 C(17)-C(16)-H(16B) 109.6

H(16A)-C(16)-H(16B) 108.1 N(2)-C(17)-H(17A) 109.2

C(16)-C(17)-H(17A) 109.2 N(2)-C(17)-H(17B) 109.2

C(16)-C(17)-H(17B) 109.2 H(17A)-C(17)-H(17B) 107.9

C(19)-C(18)-H(18A) 108.9 N(3)-C(18)-H(18A) 108.9

C(19)-C(18)-H(18B) 108.9 N(3)-C(18)-H(18B) 108.9

H(18A)-C(18)-H(18B) 107.7 C(18)-C(19)-H(19A) 109.5

C(18)-C(19)-H(19B) 109.5 H(19A)-C(19)-H(19B) 109.5

C(18)-C(19)-H(19C) 109.5 H(19A)-C(19)-H(19C) 109.5

H(19B)-C(19)-H(19C) 109.5 C(2A)-C(3A)-H(3AA) 120.4

C(4A)-C(3A)-H(3AA) 120.4 C(4A)-C(5A)-H(5AA) 120.0

C(6A)-C(5A)-H(5AA) 120.0

418



C(17)-N(2)-C(1)-C(2) 0.3(4) C(14)-N(2)-C(1)-C(2) -137.6(3)

C(17)-N(2)-C(1)-C(10) -176.0(2) C(14)-N(2)-C(1)-C(10) 46.1(3)

N(2)-C(1)-C(2)-C(3) 179.6(2) C(10)-C(1)-C(2)-C(3) -3.9(3)

C(4)-N(1)-C(3)-C(2) 178.4(2) C(11)-N(1)-C(3)-C(2) -8.4(3)

C(4)-N(1)-C(3)-C(8) -1.5(3) C(11)-N(1)-C(3)-C(8) 171.68(19)

C(1)-C(2)-C(3)-N(1) -178.5(2) C(1)-C(2)-C(3)-C(8) 1.4(3)

C(3)-N(1)-C(4)-C(5) -0.2(3) C(11)-N(1)-C(4)-C(5) -173.5(2)

N(1)-C(4)-C(5)-C(7) 2.6(3) N(1)-C(4)-C(5)-C(6) -179.3(2)

C(4)-C(5)-C(6)-O(1) 7.0(4) C(7)-C(5)-C(6)-O(1) -175.0(3)

C(4)-C(5)-C(6)-O(2) -173.9(2) C(7)-C(5)-C(6)-O(2) 4.2(4)

C(4)-C(5)-C(7)-O(3) 175.9(2) C(6)-C(5)-C(7)-O(3) -2.1(3)

C(4)-C(5)-C(7)-C(8) -3.1(3) C(6)-C(5)-C(7)-C(8) 178.8(2)

N(1)-C(3)-C(8)-C(9) -178.79(19) C(2)-C(3)-C(8)-C(9) 1.3(3)

N(1)-C(3)-C(8)-C(7) 0.8(3) C(2)-C(3)-C(8)-C(7) -179.1(2)

O(3)-C(7)-C(8)-C(9) 2.0(3) C(5)-C(7)-C(8)-C(9) -178.9(2)

O(3)-C(7)-C(8)-C(3) -177.6(2) C(5)-C(7)-C(8)-C(3) 1.5(3)

C(3)-C(8)-C(9)-C(10) -1.3(3) C(7)-C(8)-C(9)-C(10) 179.1(2)

C(8)-C(9)-C(10)-F(1) 176.6(2) C(8)-C(9)-C(10)-C(1) -1.4(4)

C(2)-C(1)-C(10)-C(9) 4.0(4) N(2)-C(1)-C(10)-C(9) -179.4(2)

C(2)-C(1)-C(10)-F(1) -174.0(2) N(2)-C(1)-C(10)-F(1) 2.6(4)

C(4)-N(1)-C(11)-C(13) -41.9(3) C(3)-N(1)-C(11)-C(13) 144.9(2)

C(4)-N(1)-C(11)-C(12) -112.2(3) C(3)-N(1)-C(11)-C(12) 74.6(3)

N(1)-C(11)-C(12)-C(13) 108.1(3) N(1)-C(11)-C(13)-C(12) -111.1(3)

C(1)-N(2)-C(14)-C(15) 82.1(3) C(17)-N(2)-C(14)-C(15) -59.7(3)

C(16)-N(3)-C(15)-C(14) -52.8(3) C(18)-N(3)-C(15)-C(14) -177.9(2)

N(2)-C(14)-C(15)-N(3) 57.1(3 C(15)-N(3)-C(16)-C(17) 51.9(3)

C(18)-N(3)-C(16)-C(17) 175.6(2) C(1)-N(2)-C(17)-C(16) -82.7(3)

C(14)-N(2)-C(17)-C(16) 59.7(3) N(3)-C(16)-C(17)-N(2) -57.0(3)

C(15)-N(3)-C(18)-C(19) -163.2(3) C(16)-N(3)-C(18)-C(19) 72.6(4)

O(1A)-C(1A)-C(2A)-C(3A) 171.7(3) C(6A)-C(1A)-C(2A)-C(3A) -5.5(4)

O(1A)-C(1A)-C(2A)-N(1A) -8.3(4) C(6A)-C(1A)-C(2A)-N(1A) 174.6(2)



C(1A)-C(2A)-C(3A)-C(4A) 2.7(4) N(1A)-C(2A)-C(3A)-C(4A) -177.3(2)

C(2A)-C(3A)-C(4A)-C(5A) 1.5(4) C(2A)-C(3A)-C(4A)-N(2A) 179.9(2)



C(3A)-C(4A)-C(5A)-C(6A) -2.2(4) N(2A)-C(4A)-C(5A)-C(6A) 179.4(2)

C(4A)-C(5A)-C(6A)-C(1A) -1.2(4) C(4A)-C(5A)-C(6A)-N(3A) -180.0(2)

O(1A)-C(1A)-C(6A)-C(5A) -172.4(3) C(2A)-C(1A)-C(6A)-C(5A) 4.7(3)

O(1A)-C(1A)-C(6A)-N(3A) 6.4(4) C(2A)-C(1A)-C(6A)-N(3A) -176.6(2)



419

Table 4.21 - Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A

O2—H2···O3 0.82 1.78 2.536 (3) 151

N3—H3A···O1A 0.91 1.87 2.724 (3) 155

N3—H3A···O7A 0.91 2.38 3.024 (3) 128

C11—H11A···O3i 0.98 2.55 3.385 (3) 144

C15—H15B···O1ii 0.97 2.35 3.312 (3) 169

C17—H17B···O3Aiii 0.97 2.56 3.458 (4) 154

C3A—H3AA···O3iv 0.93 2.55 3.331 (3) 142

C9—H9A···O4Av 0.93 2.58 3.495 (3) 170

C14—H14B···O5Avi 0.97 2.60 3.517 (4) 157

C18—H18A···O5Avii 0.97 2.50 3.451 (5) 167

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z+1;

(iv) x, y, z+1; (v) x, y, z−1; (vi) −x, −y, −z+1; (vii) −x+1,−y, −z+1.

Table 4.22 - Cg···Cg π stacking interactions,

Cg2 and Cg4 are the centroids of rings N1/C3/C8/C7/C5/C4 and

1/C2/C3/C8/C9/C10;

CgI···CgJ Cg···Cg (Å) CgI Perp (Å) Cgj Perp (Å) Slippage (Å)

Cg2···Cg2i 3.5785 (13) -3.3834 (9) -3.3834 (9) 1.16 (5)

Cg2···Cg2ii 3.7451 (12) -3.6091 (9) 3.6090 (9) 1.00 (0)

Cg2···Cg4ii 3.6587 (13) -3.3748 (9) -3.4114 (10)

[Symmetry codes: (i) -x, 1-y, -z; (ii) 1-x, 1-y, -z;]

In the crystal structure of the title compound, (XXI), there is one cation-anion

pair in the asymmetric unit (Fig. 4.7). N—H···O,O bifurcated interactions, other

interactions, packing of the molecules along a, b and c axes are shown in Figures 4.8,

4.9, 4.10, 4.11 and 4.12 respectively. One N atom in the six-membered piperazine

ring (N2/C14/C15/N3/C16/C17) in the enrofloxacinium cation is protonated which

adopts a slightly distorted chair conformation with puckering parameters Q, θ and φ

of 0.563 (3)A%, 4.0 (3)° and 358.0 (5)° (Cremer & Pople, 1975). The dihedral angles

between the mean planes of the cyclopropyl and piperazine rings with the 10-atom

ring system of the quinolone group are 48.1 (1)° and 69.9 (5)° respectively. The

picrate anion interacts with the protonated N atom of an adjacent cation through a

bifurcated N—H···O three-center hydrogen bond forming a R12(6) ring motif. The

dihedral angle between the mean planes of the anion benzene and cation piperizine,

quinoline and cyclopropyl rings are 61.3 (6)°, 31.1 (4)° and 70.4 (9)°, respectively.

The mean planes of the two o-NO2 and single p-NO2 groups in the picrate anion are

420

twisted by 6.7 (6)°, 38.3 (9)° and 12.8 (7)° with respect to the mean planes of the 6-

membered benzene ring. Bond distances and angles are in normal ranges (Allen et al.,

1987). Strong N—H···O and weak intermolecular C—H···O hydrogen bonds in

concert with weak π–π stacking interactions (Table 4.22) dominate the crystal packing

creating a 2-D network structure along 011 (Fig. 4.13).

Fig. 4.8 – N—H···(O,O) bifurcated interactions

Fig. 4.9 – Hydrogen bounding interactions in the title compound

421



422



Dashed lines Indicate N—H···O hydrogen bonds and weak C—H···O

intermolecular interactions creating a 2-D network structure along 011.

423

It may be concluded that strong N—H···O and weak intermolecular C—H···O

hydrogen bonds in concert with weak π–π stacking interactions [centroid–centroid

distances = 3.5785 (13), 3.7451 (12) and 3.6587 (13) Å] dominate the crystal packing.

Bond distances and angles are in normal ranges (Allen et al., 1987). Recently

published 2-hydroxyethanaminium enrofloxacinate (Sun et al., 2004) is the very close

structure to the present structure and the bond lengths and bond angles of

enrofloacinate ion are in good agreement compared to the present structure. No

classical hydrogen bonds found for the present structure.

* * * * *

424

Section 4.4

Crystal structure studies of etoricoxibium picrate

Abstract

In the cation of the title salt (systematic name: 5-{5-chloro-3-[4-(methylsulfonyl)

phenyl]-2-pyridyl}-2-methylpyridinium 2,4,6-trinitrophenolate), C18H16ClN2O2S+

-

C6H2N3O7-, the mean planes of the two pyridine rings in the bipyridine unitare twisted

by 33.9 (2)o with respect to each other. The dihedral angles between the mean planes

of the sulfonylbenzene ring and the chloropyridine and methylpyridine rings are 51.2

(0) and 49.3 (9)o, respectively. The picrate anion interacts with the protonated N atom

through a bifurcated N—H··· (O,O) hydrogen bond, forming an R1 (6) ring motif with

the N atom from the methylpyridine group of an adjacent cation. N—H···O hydrogen

bonds, weak C—H···O and π – π stacking interactions [centroid–centroid distances =

3.8192 (9) and 3.6749 (9)] occur in the crystal packing, creating a two-dimensional

network structure along [110]. Classic hydrogen bonds found for the present

structure.

The title compound, crystallizes in a monoclinic space group P21/c with a =

9.02500(10) Å; b = 12.74960(10) Å; c = 21.8011(3) Å; α = 90°; β = 98.1140(10)°; γ =

90°; V = 2483.43(5) Å3; Z = 4; Dcal = 1.573 Mg/m

3 at T = 123(2) K. The structure

was solved by direct methods and refined by full-matrix least-squares procedures to

final R = 0.0378 and wR2 = 0.1010 using 4932 reflections.

Introduction

Coxibs are the traditional non-steroidal anti-inflammatory drugs that counter

the positive effects of aspirin in preventing blood clots. The research, published in the

proceedings of the national academy of sciences (Rimon et al., 2010)), indicates that

people who are taking aspirin and coxibs together are in fact inhibiting the aspirin's

effectiveness in preventing heart attacks and strokes. Some of the important class of

coxib drugs are valdecoxib, celecoxib, rofecoxib, lumiracoxib, etoricoxib etc.

Etoricoxib (brand name arcoxia worldwide; also algix and tauxib in Italy) is a novel

selective COX-2 inhibitor (Patrignani et al., 2003). Like any other COX-2 selective

inhibitor, etoricoxib selectively inhibits isoform 2 of the enzyme cyclo-oxigenase

(COX-2). The crystal structure of valdecoxib, a non-steroidal anti-inflammatory drug

425

(Malathy Sony et al., 2005), a pseudopolymorph of valdecoxib (Yathirajan et al.,

2005) and celecoxib, a COX-II inhibitor (Vasu Dev et al., 1999) have been reported.

In the view of the importance of etoricoxib, this paper presents the crystal structure of

the title compound, etoricoxibium picrate.

(XXII)


Experimental

Etoricoxib (3.59 g, 0.01 mmol) and picric acid (2.29 g, 0.01 mmol) in the ratio

1:1 were mixed together in a hot methanol solution. The mixture was warmed at 330 K

for few minutes. The resultant precipitate was dried and recrystallized using DMSO

solution. Crystals of the title compound (XXII) were obtained by the slow evaporation

of DMSO solution at room temperature after few days. (m.p.: 463 – 465 K)


N

N

S

O

OCl

O

NO2

O2N NO2

H

N

N

S

O

OCl

OH

NO2O2N

NO2

+

MeOH

Reaction scheme

426

Refinement

All of the H atoms were placed in their calculated positions and then refined

using the riding model with Atom—H lengths of 0.95Å (CH), 0.98Å (CH3) or 0.88Å

(NH). Isotropic displacement parameters for these atoms were set to 1.18 times (NH),

1.18–1.22 (CH) or 1.50–1.51 (CH3) times Ueq of the parent atom.

Special details


are estimated using the full covariance matrix.The cell e.s.d.'s are taken into account








2 > σ (F

2) is used only for

calculating R factors(gt) etc. and is not relevant to the choice of reflections for



Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker,

1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97

(Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997);

molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for

publication: SHELXTL.







the hydrogen atoms.

427



indicate N —H···O hydrogen bonds between the cation and anion and

a R12(6) ring motif.

The bond lengths and bond angles involving the hydrogen atoms are listed in

Tables 4.29 and 4.30. The torsion angles are presented in Table 4.31. Table 4.32 gives

description of hydrogen-bond geometry and Cg···Cg π-stacking interactions are given

in Table 4.33.

A perspective view of the title compound is shown in Fig. 4.14 indicting N —H···O

hydrogen bonds between the cation and anion and a R12(6) ring motif.


Empirical formula C24H18ClN5O9S





Space group P 21/c

Unit cell dimensions a = 9.02500(10) Å α = 90°

b=12.74960(10)Å β =98.1140(10)°

c = 21.8011(3) Å γ = 90°

Volume 2483.43(5) Å3

428

Z 4



F(000) 1208



Index ranges -11<=h<=9, -15<=k<=15, -26<=l<=18















Atoms x y z U(eq)

Cl -2706(1) -1622(1) 3022(1) 26(1)

S 656(1) 5386(1) 3618(1) 18(1)

O(1A) 208(2) 5937(1) 4136(1) 29(1)

O(2A) 76(2) 5735(1) 3001(1) 29(1)

N(1A) 643(2) -881(1) 4323(1) 17(1)

N(2A) 4204(1) 1801(1) 4712(1) 14(1)

C(1A) -1359(2) -902(1) 3491(1) 17(1)

C(2A) -431(2) -1401(1) 3964(1) 19(1)

C(3A) 812(2) 155(1) 4231(1) 14(1)

C(4A) -172(2) 728(1) 3800(1) 14(1)

C(5A) -1249(2) 168(1) 3407(1) 16(1)

C(6A) 2160(2) 618(1) 4607(1) 14(1)

C(7A) 2985(2) 1400(1) 4370(1) 14(1)

C(8A) 4719(2) 1489(1) 5293(1) 15(1)

C(9A) 6056(2) 2039(1) 5623(1) 22(1)

C(10A) 3976(2) 670(1) 5538(1) 16(1)

C(11A) 2713(2) 237(1) 5197(1) 16(1)

C(12A) -120(2) 1893(1) 3751(1) 14(1)

429

C(13A) -36(2) 2355(1) 3179(1) 16(1)

C(14A) 140(2) 3437(1) 3139(1) 16(1)

C(15A) 218(2) 4041(1) 3675(1) 15(1)

C(16A) 51(2) 3600(1) 4244(1) 16(1)

C(17A) -134(2) 2519(1) 4279(1) 16(1)

C(18A) 2626(2) 5382(2) 3678(1) 26(1)

O(1B) 5628(2) 3425(1) 4301(1) 26(1)

O(2B) 7229(2) 5057(1) 4847(1) 36(1)

O(3B) 6532(2) 6456(1) 4329(1) 40(1)

O(4B) 7145(1) 6274(1) 2160(1) 24(1)

O(5B) 6964(2) 4771(1) 1692(1) 34(1)

O(6B) 6028(2) 1689(1) 2706(1) 27(1)

O(7B) 5888(2) 1608(1) 3684(1) 28(1)

N(1B) 6747(2) 5508(1) 4367(1) 21(1)

N(2B) 6942(2) 5319(1) 2157(1) 20(1)

N(3B) 5995(2) 2114(1) 3212(1) 19(1)

C(1B) 6069(2) 3794(1) 3832(1) 16(1)

C(2B) 6510(2) 4894(1) 3796(1) 16(1)

C(3B) 6736(2) 5395(1) 3265(1) 16(1)

C(4B) 6663(2) 4813(1) 2720(1) 17(1)

C(5B) 6415(2) 3744(1) 2716(1) 17(1)

C(6B) 6155(2) 3247(1) 3253(1) 16(1)



3)


Atoms U

11 U

22 U

33 U

23 U

13 U

12

Cl 24(1) 22(1) 30(1) -6(1) -3(1) -9(1)

S 18(1) 11(1) 23(1) 4(1) 0(1) -1(1)

O(1A) 36(1) 13(1) 39(1) -2(1) 10(1) 2(1)

O(2A) 29(1) 22(1) 32(1) 14(1) -5(1) -3(1)

N(1A) 13(1) 13(1) 24(1) 1(1) 3(1) 0(1)

N(2A) 12(1) 12(1) 19(1) 1(1) 3(1) -2(1)

C(1A) 13(1) 16(1) 22(1) -6(1) 3(1) -4(1)

C(2A) 16(1) 11(1) 29(1) -2(1) 4(1) -1(1)

C(3A) 12(1) 13(1) 17(1) -1(1) 4(1) 0(1)

C(4A) 13(1) 13(1) 18(1) -1(1) 5(1) 0(1)

C(5A) 15(1) 16(1) 17(1) -1(1) 2(1) 1(1)

C(6A) 11(1) 12(1) 19(1) -2(1) 3(1) 2(1)

C(7A) 13(1) 15(1) 15(1) 0(1) 3(1) 1(1)

C(8A) 12(1) 15(1) 18(1) -2(1) 2(1) 3(1)

C(9A) 16(1) 21(1) 29(1) -1(1) -3(1) -2(1)

C(10A) 15(1) 18(1) 17(1) 3(1) 2(1) 2(1)

C(11A) 14(1) 14(1) 20(1) 1(1) 5(1) 0(1)

C(12A) 10(1) 13(1) 20(1) 0(1) 0(1) 1(1)

C(13A) 15(1) 16(1) 17(1) -2(1) 1(1) 2(1)

C(14A) 15(1) 18(1) 15(1) 3(1) 1(1) 1(1)

430

C(15A) 11(1) 11(1) 22(1) 2(1) 0(1) 1(1)

C(16A) 17(1) 13(1) 17(1) -2(1) 2(1) 2(1)

C(17A) 16(1) 16(1) 16(1) 2(1) 2(1) 1(1)

C(18A) 18(1) 29(1) 30(1) 1(1) 0(1) -8(1)

O(1B) 33(1) 24(1) 23(1) 0(1) 10(1) -12(1)

O(2B) 53(1) 34(1) 19(1) 1(1) -3(1) -11(1)

O(3B) 60(1) 23(1) 36(1) -8(1) 7(1) 12(1)

O(4B) 24(1) 22(1) 24(1) 8(1) -1(1) -6(1)

O(5B) 54(1) 31(1) 20(1) -1(1) 12(1) -7(1)

O(6B) 33(1) 20(1) 29(1) -6(1) 4(1) -2(1)

O(7B) 35(1) 18(1) 34(1) 7(1) 14(1) 0(1)

N(1B) 22(1) 22(1) 21(1) -2(1) 5(1) -2(1)

N(2B) 17(1) 22(1) 20(1) 4(1) 0(1) -3(1)

N(3B) 14(1) 15(1) 28(1) 1(1) 3(1) -2(1)

C(1B) 10(1) 18(1) 20(1) 3(1) 1(1) -2(1)

C(2B) 12(1) 17(1) 19(1) -2(1) 0(1) 1(1)

C(3B) 11(1) 15(1) 22(1) 2(1) 0(1) 0(1)

C(4B) 12(1) 19(1) 18(1) 4(1) 1(1) -2(1)

C(5B) 12(1) 19(1) 19(1) -1(1) 0(1) -1(1)

C(6B) 11(1) 13(1) 22(1) 1(1) 1(1) -2(1)


2a*

2U

11+... + 2 h k a* b* U

12]



Cl-C(1A) 1.7363(16) S-O(1A) 1.4355(14)

S-O(2A) 1.4436(13) S-C(18A) 1.7640(19)

S-C(15A) 1.7679(16) N(1A)-C(2A) 1.333(2)

N(1A)-C(3A) 1.347(2) N(2A)-C(7A) 1.340(2)

N(2A)-C(8A) 1.348(2) C(1A)-C(5A) 1.381(2)

C(1A)-C(2A) 1.388(2) C(3A)-C(4A) 1.405(2)

C(3A)-C(6A) 1.489(2) C(4A)-C(5A) 1.398(2)

C(4A)-C(12A) 1.490(2) C(6A)-C(7A) 1.386(2)

C(6A)-C(11A) 1.400(2) C(8A)-C(10A) 1.387(2)

C(8A)-C(9A) 1.490(2) C(10A)-C(11A) 1.384(2)

C(12A)-C(13A) 1.392(2) C(12A)-C(17A) 1.402(2)

C(13A)-C(14A) 1.392(2) C(14A)-C(15A) 1.394(2)

C(15A)-C(16A) 1.388(2) C(16A)-C(17A) 1.392(2)

O(1B)-C(1B) 1.242(2) O(2B)-N(1B) 1.219(2)

O(3B)-N(1B) 1.224(2) O(4B)-N(2B) 1.2305(19)

O(5B)-N(2B) 1.234(2) O(6B)-N(3B) 1.233(2)

O(7B)-N(3B) 1.231(2) N(1B)-C(2B) 1.461(2)

N(2B)-C(4B) 1.441(2) N(3B)-C(6B) 1.452(2)

C(1B)-C(6B) 1.452(2) C(1B)-C(2B) 1.464(2)

C(2B)-C(3B) 1.361(2) C(3B)-C(4B) 1.394(2)

C(4B)-C(5B) 1.381(2) C(5B)-C(6B) 1.383(2)

431



O(1A)-S-O(2A) 118.49(9) O(1A)-S-C(18A) 109.69(9)

O(2A)-S-C(18A) 107.39(9) O(1A)-S-C(15A) 109.14(8)

O(2A)-S-C(15A) 108.00(8) C(18A)-S-C(15A) 103.01(8)

C(2A)-N(1A)-C(3A) 119.18(14) C(7A)-N(2A)-C(8A) 123.92(14)

C(5A)-C(1A)-C(2A) 120.25(15) C(5A)-C(1A)-Cl 120.11(13)

C(2A)-C(1A)-Cl 119.60(13) N(1A)-C(2A)-C(1A) 121.42(15)

N(1A)-C(3A)-C(4A) 122.41(14) N(1A)-C(3A)-C(6A) 114.07(14)

C(4A)-C(3A)-C(6A) 123.47(14) C(5A)-C(4A)-C(3A) 117.60(14)

C(5A)-C(4A)-C(12A) 119.48(14) C(3A)-C(4A)-C(12A) 122.92(14)

C(1A)-C(5A)-C(4A) 118.72(15) C(7A)-C(6A)-C(11A) 116.81(14)

C(7A)-C(6A)-C(3A) 121.39(14) C(11A)-C(6A)-C(3A) 121.65(14)

N(2A)-C(7A)-C(6A) 120.60(14) N(2A)-C(8A)-C(10A) 117.52(14)

N(2A)-C(8A)-C(9A) 117.64(15) C(10A)-C(8A)-C(9A) 124.83(15)

C(11A)-C(10A)-C(8A) 120.01(15) C(10A)-C(11A)-C(6A) 120.96(15)

C(13A)-C(12A)-C(17A) 120.20(15) C(13A)-C(12A)-C(4A) 119.49(14)

C(17A)-C(12A)-C(4A) 120.30(14) C(12A)-C(13A)-C(14A) 119.75(15)

C(13A)-C(14A)-C(15A) 119.21(15) C(16A)-C(15A)-C(14A) 121.74(15)

C(16A)-C(15A)-S 120.60(12) C(14A)-C(15A)-S 117.54(12)

C(15A)-C(16A)-C(17A) 118.62(15) C(16A)-C(17A)-C(12A) 120.24(15)

O(2B)-N(1B)-O(3B) 123.86(16) O(2B)-N(1B)-C(2B) 118.13(15)

O(3B)-N(1B)-C(2B) 117.87(15) O(4B)-N(2B)-O(5B) 123.07(15)

O(4B)-N(2B)-C(4B) 118.76(15) O(5B)-N(2B)-C(4B) 118.16(14)

O(7B)-N(3B)-O(6B) 122.22(15) O(7B)-N(3B)-C(6B) 119.13(14)

O(6B)-N(3B)-C(6B) 118.59(14) O(1B)-C(1B)-C(6B) 126.59(15)

O(1B)-C(1B)-C(2B) 121.90(15) C(6B)-C(1B)-C(2B) 111.45(14)

C(3B)-C(2B)-N(1B) 116.85(15) C(3B)-C(2B)-C(1B) 124.75(15)

N(1B)-C(2B)-C(1B) 118.40(14) C(2B)-C(3B)-C(4B) 118.66(15)

C(5B)-C(4B)-C(3B) 121.29(15) C(5B)-C(4B)-N(2B) 118.90(15)

C(3B)-C(4B)-N(2B) 119.69(15) C(4B)-C(5B)-C(6B) 119.59(16)

C(5B)-C(6B)-N(3B) 115.48(15) C(5B)-C(6B)-C(1B) 123.50(15)

N(3B)-C(6B)-C(1B) 121.01(14)




Atoms x y z U(eq)

H(2AB) 4697 2297 4547 17

H(2AA) -564 -2128 4034 23

H(5AA) -1893 515 3089 19

H(7AA) 2683 1654 3962 17

H(9AA) 6164 2722 5429 34

H(9AB) 6952 1615 5600 34

H(9AC) 5930 2140 6059 34

H(10A) 4335 405 5938 20

H(11A) 2214 -327 5366 19

H(13A) -98 1934 2816 19

432

H(14A) 206 3759 2751 19

H(16A) 63 4028 4601 19

H(17A) -269 2204 4662 19

H(18A) 2983 6096 3621 39

H(18B) 2933 4923 3357 39

H(18C) 3056 5123 4088 39

H(3BA) 6939 6126 3266 20

H(5BA) 6424 3354 2345 20



N(2A)-H(2AB) 0.8800 C(2A)-H(2AA) 0.9500

C(5A)-H(5AA) 0.9500 C(7A)-H(7AA) 0.9500

C(9A)-H(9AA) 0.9800 C(9A)-H(9AC) 0.9800

C(9A)-H(9AB) 0.9800 C(10A)-H(10A) 0.9500

C(11A)-H(11A) 0.9500 C(13A)-H(13A) 0.9500

C(14A)-H(14A) 0.9500 C(5B)-H(5BA) 0.9500

C(3B)-H(3BA) 0.9500 C(16A)-H(16A) 0.9500

C(17A)-H(17A) 0.9500 C(18A)-H(18A) 0.9800

C(18A)-H(18B) 0.9800 C(18A)-H(18C) 0.9800



C(7A)-N(2A)-H(2AB) 118.0 C(8A)-N(2A)-H(2AB) 118.0

N(1A)-C(2A)-H(2AA) 119.3 C(1A)-C(2A)-H(2AA) 119.3

C(1A)-C(5A)-H(5AA) 120.6 C(4A)-C(5A)-H(5AA) 120.6

N(2A)-C(7A)-H(7AA) 119.7 C(6A)-C(7A)-H(7AA) 119.7

C(8A)-C(9A)-H(9AA) 109.5 C(4B)-C(5B)-H(5BA) 120.2

C(6B)-C(5B)-H(5BA) 120.2 C(11A)-C(10A)-H(10A) 120.0

C(8A)-C(10A)-H(10A) 120.0 C(10A)-C(11A)-H(11A) 119.5

C(6A)-C(11A)-H(11A) 119.5 C(12A)-C(13A)-H(13A) 120.1

C(14A)-C(13A)-H(13A) 120.1 C(13A)-C(14A)-H(14A) 120.4

C(15A)-C(14A)-H(14A) 120.4 C(15A)-C(16A)-H(16A) 120.7

C(17A)-C(16A)-H(16A) 120.7 C(16A)-C(17A)-H(17A) 119.9

C(12A)-C(17A)-H(17A) 119.9 S-C(18A)-H(18A) 109.5

S-C(18A)-H(18B) 109.5 H(18A)-C(18A)-H(18B) 109.5

S-C(18A)-H(18C) 109.5 H(18A)-C(18A)-H(18C) 109.5

H(18B)-C(18A)-H(18C) 109.5 C(2B)-C(3B)-H(3BA) 120.7

C(4B)-C(3B)-H(3BA) 120.7 C(8A)-C(9A)-H(9AB) 109.5

H(9AA)-C(9A)-H(9AB) 109.5 C(8A)-C(9A)-H(9AC) 109.5

H(9AA)-C(9A)-H(9AC) 109.5 H(9AB)-C(9A)-H(9AC) 109.5

433



C(3A)-N(1A)-C(2A)-C(1A) 1.2(2) C(5A)-C(1A)-C(2A)-N(1A) -4.2(3)

Cl-C(1A)-C(2A)-N(1A) 178.19(12) C(2A)-N(1A)-C(3A)-C(4A) 4.7(2)

(2A)-N(1A)-C(3A)-C(6A) -172.79(14) N(1A)-C(3A)-C(4A)-C(5A) -7.5(2)

C(6A)-C(3A)-C(4A)-C(5A) 169.75(14) N(1A)-C(3A)-C(4A)-C(12A) 171.79(15)

C(6A)-C(3A)-C(4A)-C(12A) -10.9(2) C(2A)-C(1A)-C(5A)-C(4A) 1.2(2)

Cl-C(1A)-C(5A)-C(4A) 178.77(12) C(3A)-C(4A)-C(5A)-C(1A) 4.4(2)



C(4A)-C(3A)-C(6A)-C(11A) 150.31(15) C(8A)-N(2A)-C(7A)-C(6A) 0.2(2)

C(11A)-C(6A)-C(7A)-N(2A) -3.6(2) C(3A)-C(6A)-C(7A)-N(2A) 179.32(14)

C(7A)-N(2A)-C(8A)-C(10A) 3.2(2) C(7A)-N(2A)-C(8A)-C(9A) -177.65(15)

N(2A)-C(8A)-C(10A)-C(11A) -3.0(2) C(9A)-C(8A)-C(10A)-C(11A) -177.88(16)


C(3A)-C(6A)-C(11A)-C(10A) 179.36(14) C(5A)-C(4A)-C(12A)-C(13A) -53.2(2)

C(3A)-C(4A)-C(12A)-C(13A) 127.46(17) C(5A)-C(4A)-C(12A)-C(17A) 127.70(16)



C(13A)-C(14A)-C(15A)-C(16A) -3.2(2) C(13A)-C(14A)-C(15A)-S 172.85(12)

O(1A)-S-C(15A)-C(16A) -22.84(15) O(2A)-S-C(15A)-C(16A) -152.91(13)

C(18A)-S-C(15A)-C(16A) 93.67(14) O(1A)-S-C(15A)-C(14A) 161.04(13)

O(2A)-S-C(15A)-C(14A) 30.96(15) C(18A)-S-C(15A)-C(14A) -82.46(14)

C(14A)-C(15A)-C(16A)-C(17A) 2.8(2) S-C(15A)-C(16A)-C(17A) -173.15(12)


C(4A)-C(12A)-C(17A)-C(16A) 174.19(14) O(2B)-N(1B)-C(2B)-C(3B) -146.94(17)

O(3B)-N(1B)-C(2B)-C(3B) 28.9(2) O(2B)-N(1B)-C(2B)-C(1B) 32.3(2)

O(3B)-N(1B)-C(2B)-C(1B) -151.84(16) O(1B)-C(1B)-C(2B)-C(3B) -167.28(16)

C(6B)-C(1B)-C(2B)-C(3B) 10.0(2) O(1B)-C(1B)-C(2B)-N(1B) 13.6(2)

C(6B)-C(1B)-C(2B)-N(1B) -169.16(14) N(1B)-C(2B)-C(3B)-C(4B) 173.89(14)

C(1B)-C(2B)-C(3B)-C(4B) -5.3(2) C(2B)-C(3B)-C(4B)-C(5B) -2.1(2)

C(2B)-C(3B)-C(4B)-N(2B) -178.17(14) O(4B)-N(2B)-C(4B)-C(5B) 179.15(15)

O(5B)-N(2B)-C(4B)-C(5B) -0.7(2) O(4B)-N(2B)-C(4B)-C(3B) -4.6(2)

O(5B)-N(2B)-C(4B)-C(3B) 175.46(15) C(3B)-C(4B)-C(5B)-C(6B) 3.5(2)

N(2B)-C(4B)-C(5B)-C(6B) 179.62(14) C(4B)-C(5B)-C(6B)-N(3B) -176.48(14)

C(4B)-C(5B)-C(6B)-C(1B) 2.3(2) O(7B)-N(3B)-C(6B)-C(5B) 173.90(14)

O(6B)-N(3B)-C(6B)-C(5B) -3.5(2) O(7B)-N(3B)-C(6B)-C(1B) -4.9(2)

O(6B)-N(3B)-C(6B)-C(1B) 177.70(14) O(1B)-C(1B)-C(6B)-C(5B) 168.74(16)

C(2B)-C(1B)-C(6B)-C(5B) -8.4(2) O(1B)-C(1B)-C(6B)-N(3B) -12.5(3)

C(2B)-C(1B)-C(6B)-N(3B) 170.35(13)


D-H···A d(D-H) d(H···A) d(D···A) <(DHA)

N(2A)-H(2AB)...O(1B) 0.88 1.79 2.6588(18) 171.6

N(2A)-H(2AB)...O(7B) 0.88 2.46 2.8898(19) 110.9

C(2A)-H(2AA)...O(1A)#1 0.95 2.56 3.455(2) 156.1

C(9A)-H(9AA)...O(1B) 0.98 2.60 3.357(2) 134.4

C(13A)-H(13A)...O(2A)#2 0.95 2.35 3.294(2) 172.8

434

C(18A)-H(18C)...O(2B)#3 0.98 2.38 3.249(2) 146.9

C(5A)-H(5AA)...O(6B)#4 0.95 2.45 3.329(2) 153.3

C(7A)-H(7AA)...O(4B)#5 0.95 2.52 3.326(2) 142.7

C(3B)-H(3BA)...O(3B) 0.95 2.43 2.713(2) 96.7

C(3B)-H(3BA)...O(4B) 0.95 2.45 2.728(2) 96.6

C(5B)-H(5BA)...O(5B) 0.95 2.39 2.693(2) 97.9

C(5B)-H(5BA)...O(6B) 0.95 2.31 2.643(2) 99.9

Symmetry transformations used to generate equivalent atoms: #1 x, y-1, z #2 -x, y-1/2, -z+1/2

#3 -x+1, -y+1, -z+1, #4 x-1, y, z #5 -x+1, y-1/2, -z+1/2

Table 4.33 – Cg···Cg π-stacking interactions

Cg2, Cg3 and Cg4 are the centroids of rings N2A/C7A/C6A/C11A/C10A/C8A,

C12A—C17A and C1B—C6B

CgI···CgJ Cg···Cg (Å) CgI Perp (Å) CgJ Perp (Å) Slippage (Å)

Cg2···Cg2i 3.8192 (9) -3.4367 (6) -3.4367 (6) 1.66 (6)

Cg3···Cg4ii 3.6749 (9) 3.5169 (7) -3.3977 (6)

[Symmetry codes: (i) 1-x, -y, 1-z; (ii) -1+x, y, z]

Fig. 4.15 – N—H···(O,O) bifurcated hydrogen bonds

435

Fig. 4.16 – Hydrogen bond interactions


436



437

Fig. 4.20 - Packing diagram of the title compound viewed down the c axis.

Dashed Lines indicate N—H···O hydrogen bonds and weak C—H···O

intermolecular interactions creating a 2-D network

N—H···(O,O) bifurcated hydrogen bonds and hydrogen bond interactions are

shown in Figures 4.15 and 4.16 respectively. Packing of the molecules along a, b and

c axes are shown in Figures 4.17, 4.18 and 4.19 respectively. Fig. 4.20 shows the

packing diagram of the title compound viewed down the c axis with N—H···O

hydrogen bonds and weak C—H···O intermolecular interactions.

In the crystal structure of the title compound, C18H16ClN2O2S+. C6H2N3O7

-,

there is one cation-anion pair in the asymmetric unit (Fig. 4.14). In the cation, the

mean planes of the two pyridine rings in the bipyridine moiety are twisted by 33.9

(2)° against each other. The dihedral angle between the mean planes of the

sulfonylbenzene ring and the chloropyridine and methylpyridine rings are 51.2 (0)°

and 49.3 (9)°, respectively. The picrate anion interacts with the protonated N atom

through a bifurcated N—H···O hydrogen bond forming a R12(6) ring motif with the N

atom from the methylpyridine group of an adjacent cation. The dihedral angles

between the mean planes of the anion benzene ring and three chloropyridine,

methylpyridine and sulfonylbenzene rings of the cation are 53.9 (1)°, 49.3 (9)° and

3.8 (8)°, respectively. The mean planes of the two o-NO2 and single p-NO2 groups in

the picrate anion are twisted by 3.0 (5)°, 30.4 (7)° and 6.5 (9)° with respect to the

mean plane of the six-membered benzene ring. Bond distances and angles are in

normal ranges (Allen et al., 1987). N—H···O hydrogen bonds, weak C—H···O

(Table 4.32) and π–π stacking interactions (Table 4.33) dominate the crystal packing

creating an infinite 2-D network structure along the 110 (Fig. 4.20).

438

It may be concluded that the picrate anion interacts with the protonated N

atom through a bifurcated N—H···(O,O) hydrogen bond, forming an R1(6) ring motif

with the N atom from the methylpyridine group of an adjacent cation. N—H···O

hydrogen bonds, weak C—H···O and π – π stacking interactions [centroid–centroid

distances = 3.8192 (9) and 3.6749 (9)] occur in the crystal packing, creating a two-

dimensional network structure along [110]. Classic hydrogen bonds found for the

present structure. Bond distances and bond angles agree well with the reported

structures.

* * * * *

439

Section 4.5

Crystal structure studies of levocetirizinium dipicrate

Abstract

There are two cation–dianion pairs in the asymmetric unit of the title compound,

C21H27ClN2O32+

.2C6H2N3O7-,{systematic name: 1-[2-(carboxymethoxy)ethyl]-4-[(R)-

(4-chlorophenyl)-phenylmethyl]piperazine-1,4-diium bis(2,4,6-trinitrophenolate)}.

The piperazine group in the levocetirizinium cation is protonated at both N atoms.

The acetyl end groups form R22(8) hydrogen-bonded motifs with adjacent cations.

Each picrate anion interacts with the proponated N atom in the cation through a

bifurcated N—H···O hydrogen bond, forming R12(6) ring motifs. Strong and weak

intermolecular N—H···O and strong O—H···O hydrogen bonds, and weak π–ring and

π–π stacking interactions [centroid–centroid distance = 3.7419 (14) Å] dominate the

crystal packing, creating a three-dimensional supramolecular structure. Classic

hydrogen bonds found for the present structure.

The title compound, crystallizes in a monoclinic space group P21 with a =

11.24440(10) Å; b = 15.7720(2) Å; c = 20.6204(2) Å; α = 90°; β = 95.9980(10)°; γ =

90°; V = 3636.94(7) Å3; Z = 4; D cal = 1.547 Mg/m

3 at T = 295(2) K. The structure

was solved by direct methods and refined by full-matrix least-squares procedures to

final R1 = 0.0441 and wR2 = 0.1207 using 11120 reflections.

Introduction

Levocetirizine (as levocetirizine dihydrochloride) is a third-generation non-

sedative antihistamine, developed from the second-generation antihistamine

cetirizine. Chemically, levocetirizine is the active enantiomer of cetirizine. It is the L-

enantiomer of the cetirizine racemate. Levocetirizine works by blocking histamine

receptors. It does not prevent the actual release of histamine from mast cells, but

prevents it from binding to its receptors. This in turn prevents the release of other

allergy chemicals and increased blood supply to the area, and provides relief from the

typical symptoms of hayfever. Levocetirizine is called a non-sedating antihistamine as

it does not enter the brain in significant amounts, and is therefore unlikely to cause

drowsiness. A review on the use of levocetirizine in the management of allergic

rhinitis and skin allergies is described (Hair & Scott, 2006).

440

Recently, the crystal structures of propiverine picrate (Jasinski et al., 2009),

imatinibium dipicrate (Jasinski et al., 2010b) and chlorimipraminium picrate (Jasinski

et al., 2010a) have been reported. The present work reports the crystal structure of the

salt, C21H27ClN2O32+.2C6H2N3O7

-, formed by the interaction between 2-[2-[4-[(R)-(4-

chlorophenyl)-phenyl-methyl] piperazin-1-yl]ethoxy]acetic acid and 2,4,6-trinitrophenol

in aqueous medium.

(XXIII)


Experimental

Levocetirizine (3.89 g, 0.01 mol) was dissolved in 20 ml of methanol and picric

acid (4.58 g, 0.02 mol) was dissolved in 20 ml of methanol. Both the solutions were

mixed and stirred in a beaker at room temperature for half hour. The mixture was warmed

for 10 min at 323 K & kept aside for two days at room temperature. The formed salt was

filtered & dried in a vaccum desiccator over phosphorous pentoxide. The salt was

recrystallized from dimethylsulphoxide by slow evaporation (m.p: 454–456 K).

N

NH

OOH

O

O

O2N NO2

NO2

H

2

N

N

OOH

O

OH

O2N NO2

NO2

2+

MeOH

Cl

Cl

Reaction scheme

441

Refinement

All of the H atoms were placed in their calculated positions and then refined

using the riding model with Atom—H lengths of 1.00, 0.95Å (CH), 0.99Å (CH2),

0.93Å (NH), or 0.84Å (OH). Isotropic displacement parameters for these atoms were

set to 1.2 times (NH), 1.2 (CH, CH2) or 1.5 (OH) times Ueq of the parent atom.

Special details










2 > σ(F

2) is used only for




Computing details


PRO data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to



software used to prepare material for publication: SHELXTL







442


are listed in Tables 4.40 and 4.41. The torsion angles are presented in Table 4.42. Table

4.43 gives description of hydrogen-bond geometry. Cg···Cg π stacking interactions are

given in Table 4.44. Two cations and dianions pair in the asymmetric unit is shown in

Fig. 4.21. A perspective view of the title compound is shown in Fig. 4.22 indicating

strong and weak N—H···O intermolecular hydrogen bonds.

Fig. 4.21 – Two cations and dianions pair in the asymmetric unit



indicate strong and weak N—H···O intermolecular hydrogen bonds.

443


Empirical formula C33H31ClN8O17





Space group P 21

Unit cell dimensions a = 11.24440(10) Å α= 90°

b = 15.7720(2) Å β=95.9980(10)°

c = 20.6204(2) Å γ = 90°

Volume 3636.94(7) Å3

Z 4



F(000) 1752


Theta range for data collection 4.70 to 74.06°

Index ranges -9<=h<=13, -19<=k<=18, -25<=l<=24











Absolute structure parameter 0.058(13)


444




Atoms x y z U(eq)

Cl(1A) 14316(1) -751(1) 4606(1) 37(1)

O(1A) 5136(2) 1438(2) 6229(1) 32(1)

O(2A) 5911(3) 2584(2) 7689(1) 54(1)

O(3A) 6722(2) 2609(2) 6750(1) 39(1)

N(1A) 9545(2) 1702(2) 5305(1) 16(1)

N(2A) 6968(2) 1530(2) 5373(1) 17(1)

C(1A) 8903(2) 860(2) 5224(1) 18(1)

C(2A) 7617(2) 974(2) 4940(1) 18(1)

C(3A) 7555(2) 2381(2) 5379(1) 19(1)

C(4A) 8845(2) 2321(2) 5668(1) 16(1)

C(5A) 10771(2) 1571(2) 5685(1) 17(1)

C(6A) 11552(2) 933(2) 5381(1) 19(1)

C(7A) 12402(2) 514(2) 5809(1) 24(1)

C(8A) 13239(3) -17(2) 5571(2) 27(1)

C(9A) 13206(2) -134(2) 4906(2) 25(1)

C(10A) 12349(3) 241(2) 4472(2) 26(1)

C(11A) 11524(3) 788(2) 4710(1) 24(1)

C(12A) 11408(2) 2422(2) 5788(1) 20(1)

C(13A) 11565(3) 2778(2) 6413(1) 29(1)

C(14A) 12168(3) 3543(3) 6516(2) 39(1)

C(15A) 12637(3) 3954(2) 6003(2) 37(1)

C(16A) 12474(3) 3596(2) 5382(2) 31(1)

C(17A) 11863(3) 2837(2) 5273(1) 22(1)

C(18A) 5646(2) 1559(2) 5150(1) 26(1)

C(19A) 4949(3) 1943(2) 5654(2) 30(1)

C(20A) 4897(3) 1860(3) 6806(2) 40(1)

C(21A) 5937(3) 2386(2) 7076(2) 37(1)

Cl(1B) 1810(1) 1027(1) 8697(1) 53(1)

O(1B) 9688(2) 4379(2) 8671(1) 38(1)

O(2B) 7870(2) 3429(2) 8100(1) 39(1)

O(3B) 8678(3) 3414(2) 7157(1) 58(1)

N(1B) 5358(2) 4196(2) 9704(1) 19(1)

N(2B) 7932(2) 4264(2) 9564(1) 22(1)

C(1B) 5976(2) 3577(2) 9290(1) 20(1)

C(2B) 7275(3) 3436(2) 9538(1) 22(1)

C(3B) 7382(3) 4805(2) 10038(1) 25(1)

C(4B) 6090(3) 4992(2) 9811(1) 22(1)

C(5B) 4118(2) 4397(2) 9353(1) 22(1)

C(6B) 3450(2) 3572(2) 9196(1) 23(1)

C(7B) 3046(3) 3084(2) 9687(2) 26(1)

C(8B) 2515(3) 2303(2) 9539(2) 34(1)

C(9B) 2388(3) 2028(2) 8893(2) 37(1)

C(10B) 2738(4) 2517(3) 8400(2) 41(1)

C(11B) 3272(3) 3296(2) 8553(2) 34(1)

C(12B) 3390(3) 5021(2) 9706(2) 24(1)

C(13B) 3556(3) 5196(2) 10375(2) 29(1)

445

C(14B) 2819(3) 5781(2) 10645(2) 35(1)

C(15B) 1889(3) 6167(2) 10263(2) 42(1)

C(16B) 1725(3) 5990(2) 9599(2) 43(1)

C(17B) 2473(3) 5434(2) 9326(2) 34(1)

C(18B) 9256(3) 4166(2) 9750(2) 33(1)

C(19B) 9876(3) 3799(3) 9198(2) 40(1)

C(20B) 9815(4) 4014(3) 8058(2) 48(1)

C(21B) 8681(4) 3587(3) 7775(2) 42(1)

O(1C) 7968(2) 971(2) 6579(1) 27(1)

O(2C) 10086(3) 1450(2) 7327(1) 62(1)

O(3C) 9234(3) 1773(2) 8184(2) 58(1)

O(4C) 8609(2) -1150(2) 9139(1) 33(1)

O(5C) 7121(2) -1831(2) 8622(1) 31(1)

O(6C) 5694(2) -1082(2) 6453(1) 36(1)

O(7C) 6664(2) -214(2) 5901(1) 31(1)

N(1C) 9382(3) 1313(2) 7721(1) 40(1)

N(2C) 7885(2) -1263(2) 8658(1) 26(1)

N(3C) 6489(2) -549(2) 6415(1) 22(1)

C(1C) 7961(2) 430(2) 7020(1) 21(1)

C(2C) 8661(3) 537(2) 7646(1) 25(1)

C(3C) 8660(3) 12(2) 8169(1) 25(1)

C(4C) 7922(2) -702(2) 8104(1) 22(1)

C(5C) 7203(2) -866(2) 7534(1) 21(1)

C(6C) 7240(2) -329(2) 7005(1) 21(1)

O(1D) 9393(2) 1889(1) 4006(1) 25(1)

O(2D) 9747(3) 508(2) 3242(1) 55(1)

O(3D) 8281(2) 519(2) 2470(1) 42(1)

O(4D) 8374(2) 3003(2) 1104(1) 31(1)

O(5D) 8824(2) 4222(2) 1546(1) 38(1)

O(6D) 10061(3) 4402(2) 3830(1) 44(1)

O(7D) 9339(2) 3486(2) 4465(1) 36(1)

N(1D) 8989(3) 879(2) 2865(1) 29(1)

N(2D) 8686(2) 3447(2) 1584(1) 23(1)

N(3D) 9598(2) 3716(2) 3931(1) 24(1)

C(1D) 9264(2) 2259(2) 3470(1) 16(1)

C(2D) 9020(2) 1804(2) 2857(1) 20(1)

C(3D) 8806(2) 2181(2) 2259(1) 18(1)

C(4D) 8903(2) 3054(2) 2217(1) 18(1)

C(5D) 9179(2) 3547(2) 2769(1) 19(1)

C(6D) 9327(2) 3162(2) 3367(1) 18(1)

O(1E) 5620(2) 3989(1) 11000(1) 25(1)

O(2E) 5266(3) 5306(2) 11838(1) 51(1)

O(3E) 6761(3) 5236(2) 12589(1) 50(1)

O(4E) 6578(2) 2660(2) 13842(1) 45(1)

O(5E) 6351(2) 1451(2) 13342(1) 45(1)

O(6E) 4915(4) 1466(2) 11072(2) 66(1)

O(7E) 5555(2) 2432(2) 10466(1) 33(1)

N(1E) 6011(3) 4903(2) 12190(1) 34(1)

N(2E) 6358(2) 2233(2) 13342(1) 34(1)

N(3E) 5367(2) 2163(2) 10997(1) 28(1)

C(1E) 5733(2) 3579(2) 11521(1) 19(1)

446

C(2E) 5990(2) 3984(2) 12154(1) 22(1)

C(3E) 6207(2) 3559(2) 12732(1) 25(1)

C(4E) 6126(2) 2685(2) 12734(1) 26(1)

C(5E) 5844(2) 2231(2) 12163(1) 24(1)

C(6E) 5666(2) 2670(2) 11580(1) 20(1)

O(1F) 6833(2) 5028(1) 8453(1) 26(1)

O(2F) 4523(2) 4860(2) 7744(1) 48(1)

O(3F) 5271(3) 4344(2) 6921(2) 72(1)

O(4F) 6482(2) 7134(2) 5898(1) 32(1)

O(5F) 7981(2) 7779(2) 6431(1) 31(1)

O(6F) 9295(2) 6998(2) 8610(1) 39(1)

O(7F) 8319(2) 6105(2) 9137(1) 34(1)

N(1F) 5248(2) 4856(2) 7353(1) 30(1)

N(2F) 7192(2) 7233(2) 6387(1) 23(1)

N(3F) 8502(2) 6470(2) 8632(1) 25(1)

C(1F) 6912(2) 5561(2) 8023(1) 20(1)

C(2F) 6167(2) 5517(2) 7405(1) 22(1)

C(3F) 6259(2) 6021(2) 6876(1) 21(1)

C(4F) 7102(2) 6676(2) 6935(1) 20(1)

C(5F) 7830(2) 6799(2) 7512(1) 22(1)

C(6F) 7730(2) 6275(2) 8035(1) 22(1)



3)


Atoms U

11 U

22 U

33 U

23 U

13 U

12

Cl(1A) 23(1) 27(1) 62(1) -11(1) 10(1)

O(1A) 29(1) 37(1) 31(1) 5(1) 4(1) -2(1)

O(2A) 54(2) 69(2) 40(1) -11(1) 19(1) -23(2)

O(3A) 37(1) 47(1) 33(1) -4(1) 12(1) -10(1)

N(1A) 14(1) 22(1) 10(1) 3(1) 0(1) 2(1)

N(2A) 12(1) 23(1) 17(1) 5(1) -1(1) 0(1)

C(1A) 17(1) 21(1) 16(1) 0(1) 1(1) 1(1)

C(2A) 18(1) 23(1) 12(1) 0(1) -3(1) 1(1)

C(3A) 17(1) 21(1) 20(1) 3(1) 2(1) 4(1)

C(4A) 14(1) 21(1) 14(1) -3(1) 3(1) 0(1)

C(5A) 15(1) 24(1) 12(1) 3(1) 0(1) 3(1)

C(6A) 14(1) 22(1) 20(1) 4(1) 0(1) 1(1)

C(7A) 23(1) 26(1) 21(1) 6(1) -5(1) -1(1)

C(8A) 19(1) 25(2) 35(2) 8(1) -5(1) 4(1)

C(9A) 15(1) 17(1) 45(2) 0(1) 9(1) 3(1)

C(10A) 28(1) 29(2) 23(1) 2(1) 8(1) 3(1)

C(11A) 21(1) 27(2) 24(1) 7(1) 3(1) 8(1)

C(12A) 12(1) 27(1) 19(1) 2(1) -1(1) 0(1)

C(13A) 31(2) 39(2) 16(1) 2(1) -1(1) -9(1)

C(14A) 47(2) 43(2) 24(2) -6(2) -8(1) -13(2)

C(15A) 39(2) 34(2) 36(2) 5(1) -5(1) -10(1)

C(16A) 28(2) 33(2) 32(2) 11(1) 5(1) -2(1)

C(17A) 22(1) 24(1) 22(1) 0(1) 2(1) 4(1)

447

C(18A) 13(1) 37(2) 27(1) 7(1) -7(1) -2(1)

C(19A) 14(1) 36(2) 40(2) 10(1) 2(1) 2(1)

C(20A) 41(2) 45(2) 37(2) -2(2) 16(2) -5(2)

C(21A) 40(2) 38(2) 34(2) 2(2) 10(1) 0(2)

Cl(1B) 76(1) 33(1) 43(1) 6(1) -22(1) -14(1)

O(1B) 36(1) 42(1) 36(1) 0(1) 6(1) -7(1)

O(2B) 38(1) 46(1) 35(1) -7(1) 13(1) -4(1)

O(3B) 54(2) 81(2) 41(1) -15(2) 20(1) -28(2)

N(1B) 19(1) 24(1) 13(1) 2(1) -1(1) -1(1)

N(2B) 21(1) 28(1) 17(1) 7(1) -6(1) -4(1)

C(1B) 23(1) 24(1) 12(1) 2(1) -1(1) -2(1)

C(2B) 23(1) 25(1) 19(1) 3(1) -2(1) -3(1)

C(3B) 27(1) 27(1) 20(1) 3(1) -3(1) -9(1)

C(4B) 30(2) 20(1) 17(1) 3(1) 1(1) -2(1)

C(5B) 20(1) 31(2) 14(1) 9(1) -5(1) -2(1)

C(6B) 20(1) 29(2) 19(1) 4(1) -5(1) 2(1)

C(7B) 24(1) 31(2) 23(1) 6(1) -1(1) 3(1)

C(8B) 37(2) 28(2) 35(2) 9(1) -2(1) -3(1)

C(9B) 39(2) 28(2) 39(2) 3(1) -15(1) -7(1)

C(10B) 55(2) 42(2) 22(2) -1(2) -14(1) -9(2)

C(11B) 39(2) 39(2) 22(1) 7(1) -8(1) -10(2)

C(12B) 22(1) 24(1) 27(1) 8(1) 3(1) -1(1)

C(13B) 31(2) 33(2) 25(2) 3(1) 5(1) 3(1)

C(14B) 36(2) 32(2) 40(2) 0(1) 13(1) 3(1)

C(15B) 37(2) 26(2) 64(2) 3(2) 12(2) 4(1)

C(16B) 29(2) 34(2) 62(2) 12(2) -5(2) 8(2)

C(17B) 35(2) 32(2) 32(2) 9(1) -6(1) -1(1)

C(18B) 20(1) 45(2) 31(2) 7(1) -9(1) -4(1)

C(19B) 21(1) 47(2) 51(2) 3(2) 0(1) 0(1)

C(20B) 48(2) 57(3) 42(2) -7(2) 18(2) -17(2)

C(21B) 50(2) 43(2) 32(2) -1(2) 10(2) -9(2)

O(1C) 31(1) 30(1) 20(1) 9(1) -4(1) -4(1)

O(2C) 67(2) 88(2) 27(1) 16(1) -6(1) -52(2)

O(3C) 69(2) 38(2) 65(2) -9(1) 0(2) -11(1)

O(4C) 33(1) 43(1) 21(1) 12(1) -10(1) -7(1)

O(5C) 29(1) 37(1) 27(1) 11(1) 0(1) -9(1)

O(6C) 22(1) 57(2) 28(1) 9(1) -5(1) -15(1)

O(7C) 41(1) 35(1) 17(1) 7(1) -2(1) -7(1)

N(1C) 46(2) 42(2) 29(1) 13(1) -13(1) -15(1)

N(2C) 23(1) 31(1) 22(1) 7(1) 0(1) -2(1)

N(3C) 15(1) 31(1) 21(1) 4(1) 0(1) 2(1)

C(1C) 17(1) 28(1) 17(1) 3(1) 2(1) 2(1)

C(2C) 21(1) 31(2) 24(1) 7(1) 0(1) -5(1)

C(3C) 21(1) 32(2) 20(1) 2(1) -5(1) -1(1)

C(4C) 20(1) 30(2) 17(1) 6(1) 2(1) 0(1)

C(5C) 18(1) 26(1) 20(1) 5(1) 2(1) 0(1)

C(6C) 15(1) 30(2) 17(1) 3(1) 3(1) 3(1)

O(1D) 32(1) 27(1) 15(1) 5(1) -1(1) 7(1)

O(2D) 87(2) 29(1) 43(1) 4(1) -20(1) 21(1)

O(3D) 56(2) 28(1) 41(1) -6(1) -7(1) -5(1)

O(4D) 34(1) 43(1) 15(1) 6(1) -3(1) 4(1)

448

O(5D) 45(1) 32(1) 35(1) 19(1) -5(1) -5(1)

O(6D) 60(2) 32(1) 42(1) -14(1) 6(1) -19(1)

O(7D) 49(1) 40(1) 21(1) -8(1) 2(1) -1(1)

N(1D) 44(2) 20(1) 22(1) 1(1) 1(1) 3(1)

N(2D) 16(1) 33(1) 20(1) 9(1) 0(1) 2(1)

N(3D) 23(1) 26(1) 23(1) -5(1) -3(1) 1(1)

C(1D) 13(1) 22(1) 13(1) 2(1) 0(1) 3(1)

C(2D) 20(1) 19(1) 20(1) 1(1) 0(1) 3(1)

C(3D) 15(1) 25(1) 14(1) -1(1) -1(1) 3(1)

C(4D) 12(1) 26(1) 16(1) 7(1) 0(1) 2(1)

C(5D) 12(1) 20(1) 23(1) 6(1) 0(1) 2(1)

C(6D) 13(1) 23(1) 19(1) -4(1) -1(1) 2(1)

O(1E) 38(1) 25(1) 12(1) 2(1) 0(1) 4(1)

O(2E) 68(2) 37(1) 43(1) -12(1) -14(1) 22(1)

O(3E) 67(2) 42(2) 36(1) -18(1) -14(1) -3(1)

O(4E) 37(1) 81(2) 17(1) 12(1) 0(1) 9(1)

O(5E) 32(1) 61(2) 40(1) 31(1) -5(1) -7(1)

O(6E) 112(3) 38(2) 48(2) -6(1) 10(2) -37(2)

O(7E) 51(1) 32(1) 15(1) -1(1) -1(1) -6(1)

N(1E) 44(2) 34(2) 23(1) -12(1) -3(1) 7(1)

N(2E) 13(1) 65(2) 23(1) 17(1) 2(1) 1(1)

N(3E) 32(1) 23(1) 28(1) -2(1) 0(1) -5(1)

C(1E) 15(1) 27(1) 16(1) 1(1) 0(1) 4(1)

C(2E) 19(1) 27(2) 20(1) -3(1) 1(1) 4(1)

C(3E) 14(1) 49(2) 12(1) -5(1) 2(1) 3(1)

C(4E) 13(1) 47(2) 18(1) 11(1) 3(1) 3(1)

C(5E) 15(1) 30(2) 26(1) 9(1) 1(1) -2(1)

C(6E) 15(1) 25(1) 18(1) 1(1) 0(1) -2(1)

O(1F) 26(1) 29(1) 22(1) 9(1) -2(1) 2(1)

O(2F) 45(1) 60(2) 40(1) 3(1) 8(1) -25(1)

O(3F) 86(2) 67(2) 64(2) -34(2) 18(2) -36(2)

O(4F) 31(1) 46(1) 18(1) 8(1) -6(1) -8(1)

O(5F) 22(1) 43(1) 27(1) 12(1) 3(1) -8(1)

O(6F) 22(1) 64(2) 30(1) 11(1) -5(1) -14(1)

O(7F) 43(1) 41(1) 18(1) 9(1) -5(1) -9(1)

N(1F) 38(1) 32(1) 19(1) 5(1) -5(1) -9(1)

N(2F) 18(1) 34(1) 18(1) 4(1) 3(1) 0(1)

N(3F) 19(1) 37(1) 19(1) 3(1) -1(1) 1(1)

C(1F) 18(1) 28(1) 15(1) 3(1) 5(1) 6(1)

C(2F) 22(1) 25(1) 19(1) -2(1) 3(1) 0(1)

C(3F) 19(1) 30(1) 14(1) 0(1) 1(1) 2(1)

C(4F) 14(1) 31(2) 16(1) 4(1) 4(1) 4(1)

C(5F) 14(1) 33(2) 19(1) 2(1) 3(1) 2(1)

C(6F) 15(1) 31(2) 20(1) 2(1) 0(1) 4(1)


2a*

2U

11+... + 2 h k a* b* U

12]

449



Cl(1A)-C(9A ) 1.745(3) O(1A)-C(20A) 1.413(4)

O(1A)-C(19A) 1.425(4) O(2A)-C(21A) 1.306(4)

O(3A)-C(21A) 1.216(4) N(1A)-C(4A) 1.502(3)

N(1A)-C(1A) 1.512(3) N(1A)-C(5A) 1.526(3)

N(2A)-C(3A) 1.495(4) N(2A)-C(2A) 1.495(3)

N(2A)-C(18A) 1.510(3) C(1A)-C(2A) 1.513(3)

C(3A)-C(4A) 1.512(3) C(5A)-C(6A) 1.514(4)

C(5A)-C(12A) 1.525(4) C(6A)-C(7A) 1.398(4)

C(6A)-C(11A) 1.399(4) C(7A)-C(8A) 1.386(4)

C(8A)-C(9A) 1.381(5) C(9A)-C(10A) 1.376(4)

C(10A)-C(11A) 1.393(4) C(12A)-C(17A) 1.390(4)

C(12A)-C(13A) 1.400(4) C(13A)-C(14A) 1.390(5)

C(14A)-C(15A) 1.390(5) C(15A)-C(16A) 1.394(5)

C(16A)-C(17A) 1.387(5) C(18A)-C(19A) 1.494(5)

C(20A)-C(21A) 1493(5) l(1B)-C(9B) 1.739(3

O(1B)-C(20B) 1.410(4 O(1B)-C(19B) 1.419(4)

O(2B)-C(21B) 1.211(4) O(3B)-C(21B) 1.304(4)

N(1B)-C(4B) 1.505(4) N(1B)-C(1B) 1.512(4)

N(1B)-C(5B) 1.535(3) N(2B)-C(3B) 1.481(4)

N(2B)-C(2B) 1.499(4) N(2B)-C(18B) 1.505(4)

C(1B)-C(2B) 1.512(4) C(3B)-C(4B) 1.508(4)

C(5B)-C(12B) 1.514(4) C(5B)-C(6B) 1.520(4)

C(6B)-C(7B) 1.386(4) C(7B)-C(8B) 1.388(5)

C(8B)-C(9B) 1.394(5) C(9B)-C(10B) 1.367(5)

C(10B)-C(11B) 1.388(5) C(12B)-C(17B) 1.389(4)

C(12B)-C(13B) 1.400(4) C(13B)-C(14B) 1.394(5)

C(14B)-C(15B) 1.382(5) C(15B)-C(16B) 1.390(6)

C(16B)-C(17B) 1.376(5) C(18B)-C(19B) 1.510(5)

C(20B)-C(21B) 1.505(5) O(1C)-C(1C) 1.248(4)

O(2C)-N(1C) 1.213(4) O(3C)-N(1C) 1.224(4)

O(4C)-N(2C) 1.228(3) O(5C)-N(2C) 1.239(3)

O(6C)-N(3C) 1.236(3) O(7C)-N(3C) 1.220(3)

N(1C)-C(2C) 1.467(4) N(2C)-C(4C) 1.449(4)

N(3C)-C(6C) 1.448(4) C(1C)-C(6C) 1.444(4)

C(1C)-C(2C) 1.448(4) C(2C)-C(3C) 1.360(4)

C(3C)-C(4C) 1.398(4) C(4C)-C(5C) 1.378(4)

C(5C)-C(6C) 1.386(4) O(1D)-C(1D) 1.246(3)

O(2D)-N(1D) 1.238(4) O(3D)-N(1D) 1.218(4)

O(4D)-N(2D) 1.232(3) O(5D)-N(2D) 1.235(4)

O(6D)-N(3D) 1.228(4) O(7D)-N(3D) 1.222(3)

N(1D)-C(2D) 1.460(4) N(2D)-C(4D) 1.443(3)

N(3D)-C(6D) 1.460(4) C(1D)-C(6D) 1.442(4)

C(1D)-C(2D) 1.454(4) C(2D)-C(3D) 1.368(4)

C(3D)-C(4D) 1.384(4) C(4D)-C(5D) 1.388(4)

C(5D)-C(6D) 1.368(4) O(1E)-C(1E) 1.249(3)

O(2E)-N(1E) 1.227(4) O(3E)-N(1E) 1.232(4)

O(4E)-N(2E) 1.235(4) O(5E)-N(2E) 1.235(4)

O(6E)-N(3E) 1.227(4) O(7E)-N(3E) 1.212(3)

450

N(1E)-C(2E) 1.451(4) N(2E)-C(4E) 1.441(4)

N(3E)-C(6E) 1.454(4) C(1E)-C(6E) 1.442(4)

C(1E)-C(2E) 1.454(4) C(2E)-C(3E) 1.368(4)

C(3E)-C(4E) 1.382(5) C(4E)-C(5E) 1.387(5)

C(5E)-C(6E) 1.383(4) O(1F)-C(1F) 1.231(4)

O(2F)-N(1F) 1.206(4) O(3F)-N(1F) 1.205(4)

O(4F)-N(2F) 1.228(3) O(5F)-N(2F) 1.233(3)

O(6F)-N(3F) 1.224(4) O(7F)-N(3F) 1.228(3)

N(1F)-C(2F) 1.465(4) N(2F)-C(4F) 1.443(4)

N(3F)-C(6F) 1.462(4) C(1F)-C(2F) 1.453(4)

C(1F)-C(6F) 1.453(4) C(2F)-C(3F) 1.361(4)

C(3F)-C(4F) 1.399(4) C(4F)-C(5F) 1.386(4)

C(5F)-C(6F) 1.372(4)



C(20A)-O(1A)-C(19A) 114.4(3) C(4A)-N(1A)-C(1A) 110.86(19)

C(4A)-N(1A)-C(5A) 108.93(19) C(1A)-N(1A)-C(5A) 109.52(19)

C(3A)-N(2A)-C(2A) 106.79(19) C(3A)-N(2A)-C(18A) 113.3(2)

C(2A)-N(2A)-C(18A) 111.2(2) N(1A)-C(1A)-C(2A) 111.4(2)

N(2A)-C(2A)-C(1A) 110.2(2) N(2A)-C(2A)-H(2AA) 109.6

N(2A)-C(3A)-C(4A) 110.6(2) N(1A)-C(4A)-C(3A) 112.1(2)

C(6A)-C(5A)-C(12A) 111.0(2) C(6A)-C(5A)-N(1A) 114.1(2)

C(12A)-C(5A)-N(1A) 109.8(2) C(7A)-C(6A)-C(11A) 119.3(3)

C(7A)-C(6A)-C(5A) 116.2(2) C(11A)-C(6A)-C(5A) 124.4(2)

C(8A)-C(7A)-C(6A) 120.5(3) C(9A)-C(8A)-C(7A) 118.9(3)

C(10A)-C(9A)-C(8A) 122.1(3) C(10A)-C(9A)-Cl(1A) 119.2(2)

C(8A)-C(9A)-Cl(1A) 118.7(2) C(9A)-C(10A)-C(11A) 118.9(3)

C(10A)-C(11A)-C(6A) 120.2(3) C(17A)-C(12A)-C(13A) 119.5(3)

C(17A)-C(12A)-C(5A) 120.8(2) C(13A)-C(12A)-C(5A) 119.6(2)

C(14A)-C(13A)-C(12A) 120.1(3) C(13A)-C(14A)-C(15A) 120.4(3)

C(14A)-C(15A)-C(16A) 119.1(3) C(17A)-C(16A)-C(15A) 120.9(3)

C(16A)-C(17A)-C(12A) 119.9(3) C(19A)-C(18A)-N(2A) 111.9(2)

O(1A)-C(19A)-C(18A) 108.0(3) O(1A)-C(20A)-C(21A) 111.4(3)

O(3A)-C(21A)-O(2A) 123.8(3) O(3A)-C(21A)-C(20A) 122.7(3)

O(2A)-C(21A)-C(20A) 113.4(3) C(20B)-O(1B)-C(19B) 113.8(3)

C(4B)-N(1B)-C(1B) 110.2(2) C(4B)-N(1B)-C(5B) 110.7(2)

C(1B)-N(1B)-C(5B) 108.4(2) C(3B)-N(2B)-C(2B) 106.7(2)

C(3B)-N(2B)-C(18B) 111.2(2) C(2B)-N(2B)-C(18B) 113.0(2)

N(1B)-C(1B)-C(2B) 112.9(2) N(2B)-C(2B)-C(1B) 109.9(2)

N(2B)-C(3B)-C(4B) 111.3(2) N(1B)-C(4B)-C(3B) 112.1(2)

C(12B)-C(5B)-C(6B) 112.3(2) C(12B)-C(5B)-N(1B) 114.7(2)

C(6B)-C(5B)-N(1B) 109.2(2) C(7B)-C(6B)-C(11B) 119.8(3)

C(7B)-C(6B)-C(5B) 120.8(3) C(11B)-C(6B)-C(5B) 119.4(3)

C(6B)-C(7B)-C(8B) 120.0(3) C(7B)-C(8B)-C(9B) 118.9(3)

C(10B)-C(9B)-C(8B) 121.8(3) C(10B)-C(9B)-Cl(1B) 117.9(3)

C(8B)-C(9B)-Cl(1B) 120.2(3) C(9B)-C(10B)-C(11B) 118.8(3)

C(10B)-C(11B)-C(6B) 120.6(3) C(17B)-C(12B)-C(13B) 118.5(3)

C(17B)-C(12B)-C(5B) 116.1(3) C(13B)-C(12B)-C(5B) 125.3(3)

451

C(14B)-C(13B)-C(12B) 120.0(3) C(15B)-C(14B)-C(13B) 120.7(3)

C(14B)-C(15B)-C(16B) 119.2(3) C(17B)-C(16B)-C(15B) 120.5(3)

C(16B)-C(17B)-C(12B) 121.2(3) N(2B)-C(18B)-C(19B) 111.7(3)

O(1B)-C(19B)-C(18B) 106.6(3) O(1B)-C(20B)-C(21B) 111.6(3)

O(2B)-C(21B)-O(3B) 124.9(4) O(2B)-C(21B)-C(20B) 122.3(3)

O(3B)-C(21B)-C(20B) 112.8(3) O(2C)-N(1C)-O(3C) 124.7(3)

O(2C)-N(1C)-C(2C) 118.0(3) O(3C)-N(1C)-C(2C) 117.3(3)

O(4C)-N(2C)-O(5C) 123.3(2) O(4C)-N(2C)-C(4C) 118.6(2)

O(5C)-N(2C)-C(4C) 118.1(2) O(7C)-N(3C)-O(6C) 122.2(2)

O(7C)-N(3C)-C(6C) 119.6(2) O(6C)-N(3C)-C(6C) 118.2(2)

O(1C)-C(1C)-C(6C) 126.6(2) O(1C)-C(1C)-C(2C) 121.6(3)

C(6C)-C(1C)-C(2C) 111.6(2) C(3C)-C(2C)-C(1C) 126.1(3)

C(3C)-C(2C)-N(1C) 118.0(3) C(1C)-C(2C)-N(1C) 115.8(3)

C(2C)-C(3C)-C(4C) 117.7(3) C(5C)-C(4C)-C(3C) 121.5(3)

C(5C)-C(4C)-N(2C) 119.7(3) C(3C)-C(4C)-N(2C) 118.8(2)

C(4C)-C(5C)-C(6C) 119.6(3) C(5C)-C(6C)-C(1C) 123.5(2)

C(5C)-C(6C)-N(3C) 116.9(3) C(1C)-C(6C)-N(3C) 119.6(2)

O(3D)-N(1D)-O(2D) 123.9(3) O(3D)-N(1D)-C(2D) 118.2(3)

O(2D)-N(1D)-C(2D) 117.6(3) O(4D)-N(2D)-O(5D) 122.6(2)

O(4D)-N(2D)-C(4D) 119.2(3) O(5D)-N(2D)-C(4D) 118.2(3)

O(7D)-N(3D)-O(6D) 124.0(3) O(7D)-N(3D)-C(6D) 119.3(3)

O(6D)-N(3D)-C(6D) 116.7(2) O(1D)-C(1D)-C(6D) 126.1(2)

O(1D)-C(1D)-C(2D) 122.3(3) C(6D)-C(1D)-C(2D) 111.6(2)

C(3D)-C(2D)-C(1D) 124.7(3) C(3D)-C(2D)-N(1D) 116.3(3)

C(1D)-C(2D)-N(1D) 119.1(2) C(2D)-C(3D)-C(4D) 118.8(3)

C(3D)-C(4D)-C(5D) 121.2(2) C(3D)-C(4D)-N(2D) 118.5(3)

C(5D)-C(4D)-N(2D) 120.3(3) C(6D)-C(5D)-C(4D) 119.2(3)

C(5D)-C(6D)-C(1D) 124.5(3) C(5D)-C(6D)-N(3D) 116.6(3)

C(1D)-C(6D)-N(3D) 118.9(2) O(2E)-N(1E)-O(3E) 123.4(3)

O(2E)-N(1E)-C(2E) 118.7(3) O(3E)-N(1E)-C(2E) 117.8(3)

O(5E)-N(2E)-O(4E) 123.1(3) O(5E)-N(2E)-C(4E) 119.6(3)

O(4E)-N(2E)-C(4E) 117.4(3) O(7E)-N(3E)-O(6E) 122.7(3)

O(7E)-N(3E)-C(6E) 120.5(2) O(6E)-N(3E)-C(6E) 116.8(3)

O(1E)-C(1E)-C(6E) 125.9(3) O(1E)-C(1E)-C(2E) 122.5(3)

C(6E)-C(1E)-C(2E) 111.6(2) C(3E)-C(2E)-N(1E) 116.4(3)

C(3E)-C(2E)-C(1E) 124.5(3) N(1E)-C(2E)-C(1E) 119.1(3)

C(2E)-C(3E)-C(4E) 119.1(3) C(3E)-C(4E)-C(5E) 121.4(3)

C(3E)-C(4E)-N(2E) 119.4(3) C(5E)-C(4E)-N(2E) 119.2(3)

C(6E)-C(5E)-C(4E) 118.6(3) C(5E)-C(6E)-C(1E) 124.5(3)

C(5E)-C(6E)-N(3E) 116.3(3) C(1E)-C(6E)-N(3E) 119.1(2)

O(3F)-N(1F)-O(2F) 124.5(3) O(3F)-N(1F)-C(2F) 117.5(3)

O(2F)-N(1F)-C(2F) 117.9(3) O(4F)-N(2F)-O(5F) 123.4(2)

O(4F)-N(2F)-C(4F) 118.2(2) O(5F)-N(2F)-C(4F) 118.5(2)

O(6F)-N(3F)-O(7F) 122.5(2) O(6F)-N(3F)-C(6F) 118.9(2)

O(7F)-N(3F)-C(6F) 118.6(2) O(1F)-C(1F)-C(2F) 121.4(3)

O(1F)-C(1F)-C(6F) 127.6(3) C(2F)-C(1F)-C(6F) 110.9(2)

C(3F)-C(2F)-C(1F) 126.2(3) C(3F)-C(2F)-N(1F) 118.0(2)

C(1F)-C(2F)-N(1F) 115.8(2) C(2F)-C(3F)-C(4F) 118.0(2)

C(5F)-C(4F)-C(3F) 120.7(3) C(5F)-C(4F)-N(2F) 120.3(3)

C(3F)-C(4F)-N(2F) 119.0(2) C(6F)-C(5F)-C(4F) 120.1(3)

C(5F)-C(6F)-C(1F) 123.9(3) C(5F)-C(6F)-N(3F) 116.4(3)

C(1F)-C(6F)-N(3F) 119.7(2)

452




Atoms x y z U(eq)

H(2AD) 6533 2854 7821 80

H(1AC) 9645 1922 4896 19

H(2AC) 7070 1310 5793 21

H(1AA) 8923 577 5653 21

H(1AB) 9322 491 4933 21

H(2AA) 7593 1232 4501 22

H(2AB) 7218 414 4894 22

H(3AA) 7120 2781 5639 23

H(3AB) 7521 2602 4928 23

H(4AA) 9221 2887 5658 19

H(4AB) 8872 2142 6130 19

H(5AA) 10633 1349 6125 20

H(7AA) 12406 593 6265 28

H(8AA) 13825 -295 5861 32

H(10A) 12321 128 4018 31

H(11A) 10941 1063 4416 29

H(13A) 11260 2496 6768 35

H(14A) 12260 3788 6939 47

H(15A) 13063 4471 6075 44

H(16A) 12787 3875 5029 37

H(17A) 11754 2601 4847 27

H(18A) 5514 1894 4743 31

H(18B) 5353 976 5053 31

H(19A) 5221 2531 5749 36

H(19B) 4088 1957 5494 36

H(20A) 4714 1436 7135 48

H(20B) 4187 2228 6712 48

H(3BC) 8046 3154 7025 86

H(1BC) 5269 3949 1010 23

H(2BC) 7814 4518 9156 27

H(1BA) 5926 3792 8837 24

H(1BB) 5549 3027 9282 24

H(2BA) 7332 3180 9978 27

H(2BB) 7642 3039 9244 27

H(3BA) 7831 5344 10096 30

H(3BB) 7433 4515 10466 30

H(4BA) 5748 5349 10140 27

H(4BB) 6047 5317 9398 27

H(5BA) 4251 4663 8927 26

H(7BA) 3131 3283 10124 32

H(8BA) 2244 1961 9873 41

H(10B) 2618 2328 7961 49

H(11B) 3517 3643 8215 41

H(13B) 4170 4916 10645 35

H(14B) 2957 5916 11095 42

H(15B) 1369 6548 10452 50

H(16B) 1091 6255 9332 51

453

H(17B) 2361 5331 8870 41

H(18C) 9391 3790 10135 39

H(18D) 9607 4727 9871 39

H(19C) 10741 3730 9333 47

H(19D) 9535 3238 9070 47

H(20C) 10471 3593 8105 58

H(20D) 10034 4461 7755 58

H(3CA) 9145 127 8564 30

H(5CA) 6686 -1344 7505 25

H(3DA) 8595 1850 1879 22

H(5DA) 9264 4143 2733 22

H(3EA) 6411 3861 13127 30

H(5EA) 5775 1631 12172 29

H(3FA) 5766 5930 6480 25

H(5FA) 8398 7246 7546 26



O(2A)-H(2AD) 0.8400 N(1A)-H(1AC) 0.9300

N(2A)-H(2AC) 0.9300 C(1A)-H(1AA) 0.9900

C(1A)-H(1AB) 0.9900 C(2A)-H(2AA) 0.9900

C(2A)-H(2AB) 0.9900 C(3A)-H(3AA) 0.9900

C(3A)-H(3AB) 0.9900 C(4A)-H(4AA) 0.9900

C(4A)-H(4AB) 0.9900 C(5A)-H(5AA) 1.0000

C(7A)-H(7AA) 0.9500 C(8A)-H(8AA) 0.9500

C(5D)-H(5DA) 0.9500 C(13A)-H(13A) 0.9500

C(14A)-H(14A) 0.9500 C(15A)-H(15A) 0.9500

C(16A)-H(16A) 0.9500 C(17A)-H(17A) 0.9500

C(18A)-H(18A) 0.9900 C(18A)-H(18B) 0.9900

C(19A)-H(19A) 0.9900 C(19A)-H(19B) 0.9900

C(20A)-H(20A) 0.9900 C(20A)-H(20B) 0.9900

O(3B)-H(3BC) 0.8400 N(1B)-H(1BC) 0.9300

N(2B)-H(2BC) 0.9300 C(1B)-H(1BA) 0.9900

C(1B)-H(1BB) 0.9900 C(2B)-H(2BA) 0.9900

C(2B)-H(2BB) 0.9900 N(2A)-C(3A)-H(3AB) 109.5

C(4A)-C(3A)-H(3AB) 109.5 H(3AA)-C(3A)-H(3AB) 108.1

N(1A)-C(4A)-H(4AA) 109.2 C(3A)-C(4A)-H(4AA) 109.2

N(1A)-C(4A)-H(4AB) 109.2 C(3A)-C(4A)-H(4AB) 109.2

H(4AA)-C(4A)-H(4AB) 107.9 C(6A)-C(5A)-H(5AA) 107.2

C(12A)-C(5A)-H(5AA) 107.2 N(1A)-C(5A)-H(5AA) 107.2

C(8A)-C(7A)-H(7AA) 119.8 C(6A)-C(7A)-H(7AA) 119.8

C(9A)-C(8A)-H(8AA) 120.6 C(7A)-C(8A)-H(8AA) 120.6

C(9A)-C(10A)-H(10A) 120.5 C(11A)-C(10A)-H(10A) 120.5

C(3B)-H(3BA) 0.9900 C(3B)-H(3BB) 0.9900

C(4B)-H(4BA) 0.9900 C(4B)-H(4BB) 0.9900

C(5B)-H(5BA) 1.0000 C(8B)-H(8BA) 0.9500

C(10B)-H(10B) 0.9500 C(11B)-H(11B) 0.9500

C(13B)-H(13B) 0.9500 C(14B)-H(14B) 0.9500

C(15B)-H(15B) 0.9500 C(16B)-H(16B) 0.9500

454

C(17B)-H(17B) 0.9500 C(18B)-H(18C) 0.9900

C(5F)-H(5FA) 0.9500 C(3F)-H(3FA) 0.9500

C(5E)-H(5EA) 0.9500 C(3E)-H(3EA) 0.9500

C(18B)-H(18D) 0.9900 C(19B)-H(19C) 0.9900

C(19B)-H(19D) 0.9900 C(20B)-H(20D) 0.9900

C(20B)-H(20C) 0.9900 C(3C)-H(3CA) 0.9500

C(5C)-H(5CA) 0.9500 C(3D)-H(3DA) 0.9500

C(10A)-H(10A) 0.9500 C(11A)-H(11A) 0.9500



C(21A)-O(2A)-H(2AD) 109.5 C(4A)-N(1A)-H(1AC) 109.2

C(1A)-N(1A)-H(1AC) 109.2 C(5A)-N(1A)-H(1AC) 109.2

C(3A)-N(2A)-H(2AC) 108.5 C(2A)-N(2A)-H(2AC) 108.5

C(18A)-N(2A)-H(2AC) 108.5 N(1A)-C(1A)-H(1AA) 109.3

C(2A)-C(1A)-H(1AA) 109.3 N(1A)-C(1A)-H(1AB) 109.3


C(1A)-C(2A)-H(2AA) 109.6 N(2A)-C(2A)-H(2AB) 109.6


N(2A)-C(3A)-H(3AA) 109.5 C(4A)-C(3A)-H(3AA) 109.5

N(2A)-C(3A)-H(3AB) 109.5 C(4A)-C(3A)-H(3AB) 109.5

H(3AA)-C(3A)-H(3AB) 108.1 N(1A)-C(4A)-H(4AA) 109.2

C(3A)-C(4A)-H(4AA) 109.2 N(1A)-C(4A)-H(4AB) 109.2


C(6A)-C(5A)-H(5AA) 107.2 C(12A)-C(5A)-H(5AA) 107.2

N(1A)-C(5A)-H(5AA) 107.2 C(8A)-C(7A)-H(7AA) 119.8

C(6A)-C(7A)-H(7AA) 119.8 C(9A)-C(8A)-H(8AA) 120.6

C(7A)-C(8A)-H(8AA) 120.6 C(9A)-C(10A)-H(10A) 120.5

C(11A)-C(10A)-H(10A) 120.5 C(10A)-C(11A)-H(11A) 119.9

C(6A)-C(11A)-H(11A) 119.9 C(14A)-C(13A)-H(13A) 119.9

C(12A)-C(13A)-H(13A) 119.9 C(13A)-C(14A)-H(14A) 119.8

C(15A)-C(14A)-H(14A) 119.8 C(14A)-C(15A)-H(15A) 120.4

C(16A)-C(15A)-H(15A) 120.4 C(17A)-C(16A)-H(16A) 119.5

C(15A)-C(16A)-H(16A) 119.5 C(16A)-C(17A)-H(17A) 120.1

C(12A)-C(17A)-H(17A) 120.1 C(19A)-C(18A)-H(18A) 109.2

N(2A)-C(18A)-H(18A) 109.2 C(19A)-C(18A)-H(18B) 109.2

N(2A)-C(18A)-H(18B) 109.2 H(18A)-C(18A)-H(18B) 107.9

O(1A)-C(19A)-H(19A) 110.1 C(18A)-C(19A)-H(19A) 110.1

O(1A)-C(19A)-H(19B) 110.1 C(18A)-C(19A)-H(19B) 110.1

H(19A)-C(19A)-H(19B) 108.4 O(1A)-C(20A)-H(20A) 109.3

C(21A)-C(20A)-H(20A) 109.3 O(1A)-C(20A)-H(20B) 109.3

C(21A)-C(20A)-H(20B) 109.3 H(20A)-C(20A)-H(20B) 108.0

C(21B)-O(3B)-H(3BC) 109.5 C(4B)-N(1B)-H(1BC) 109.2

C(1B)-N(1B)-H(1BC) 109.2 C(5B)-N(1B)-H(1BC) 109.2

C(3B)-N(2B)-H(2BC) 108.6 C(2B)-N(2B)-H(2BC) 108.6

C(18B)-N(2B)-H(2BC) 108.6 N(1B)-C(1B)-H(1BA) 109.0

C(2B)-C(1B)-H(1BA) 109.0 N(1B)-C(1B)-H(1BB) 109.0

C(2B)-C(1B)-H(1BB) 109.0 H(1BA)-C(1B)-H(1BB) 107.8

N(2B)-C(2B)-H(2BA) 109.7 C(1B)-C(2B)-H(2BA) 109.7

N(2B)-C(2B)-H(2BB) 109.7 C(1B)-C(2B)-H(2BB) 109.7

455

H(2BA)-C(2B)-H(2BB) 108.2 N(2B)-C(3B)-H(3BA) 109.4

C(4B)-C(3B)-H(3BA) 109.4 N(2B)-C(3B)-H(3BB) 109.4

C(4B)-C(3B)-H(3BB) 109.4 H(3BA)-C(3B)-H(3BB) 108.0

N(1B)-C(4B)-H(4BA) 109.2 C(3B)-C(4B)-H(4BA) 109.2

N(1B)-C(4B)-H(4BB) 109.2 C(3B)-C(4B)-H(4BB) 109.2

H(4BA)-C(4B)-H(4BB) 107.9 C(12B)-C(5B)-H(5BA) 106.7

C(6B)-C(5B)-H(5BA) 106.7 N(1B)-C(5B)-H(5BA) 106.7

C(6B)-C(7B)-H(7BA) 120.0 C(8B)-C(7B)-H(7BA) 120.0

C(7B)-C(8B)-H(8BA) 120.5 C(9B)-C(8B)-H(8BA) 120.5

C(9B)-C(10B)-H(10B) 120.6 C(11B)-C(10B)-H(10B) 120.6

C(10B)-C(11B)-H(11B) 119.7 C(6B)-C(11B)-H(11B) 119.7

C(14B)-C(13B)-H(13B) 120.0 C(12B)-C(13B)-H(13B) 120.0

C(15B)-C(14B)-H(14B) 119.7 C(13B)-C(14B)-H(14B) 119.7

C(14B)-C(15B)-H(15B) 120.4 C(16B)-C(15B)-H(15B) 120.4

C(17B)-C(16B)-H(16B) 119.8 C(15B)-C(16B)-H(16B) 119.8

C(16B)-C(17B)-H(17B) 119.4 C(12B)-C(17B)-H(17B) 119.4

N(2B)-C(18B)-H(18C) 109.3 C(19B)-C(18B)-H(18C) 109.3

N(2B)-C(18B)-H(18D) 109.3 C(19B)-C(18B)-H(18D) 109.3

H(18C)-C(18B)-H(18D) 107.9 O(1B)-C(19B)-H(19C) 110.4

C(18B)-C(19B)-H(19C) 110.4 O(1B)-C(19B)-H(19D) 110.4

C(18B)-C(19B)-H(19D) 110.4 H(19C)-C(19B)-H(19D) 108.6

O(1B)-C(20B)-H(20C) 109.3 C(21B)-C(20B)-H(20C) 109.3

O(1B)-C(20B)-H(20D) 109.3 C(21B)-C(20B)-H(20D) 109.3

H(20C)-C(20B)-H(20D) 108.0 C(2C)-C(3C)-H(3CA) 121.2

C(4C)-C(3C)-H(3CA) 121.2 C(4C)-C(5C)-H(5CA) 120.2

C(6C)-C(5C)-H(5CA) 120.2 C(2D)-C(3D)-H(3DA) 120.6

C(4D)-C(3D)-H(3DA) 120.6 C(6D)-C(5D)-H(5DA) 120.4

C(4D)-C(5D)-H(5DA) 120.4 C(2E)-C(3E)-H(3EA) 120.4

C(4E)-C(3E)-H(3EA) 120.4 C(6E)-C(5E)-H(5EA) 120.7

C(4E)-C(5E)-H(5EA) 120.7 C(6F)-C(5F)-H(5FA) 119.9

C(4F)-C(5F)-H(5FA) 119.9 C(2F)-C(3F)-H(3FA) 121.0

C(4F)-C(3F)-H(3FA) 121.0



C(4A)-N(1A)-C(1A)-C(2A) 51.3(3) C(5A)-N(1A)-C(1A)-C(2A) 171.5(2)


N(1A)-C(1A)-C(2A)-N(2A) -59.0(3) C(2A)-N(2A)-C(3A)-C(4A) -62.8(3)


C(5A)-N(1A)-C(4A)-C(3A) -171.2(2) N(2A)-C(3A)-C(4A)-N(1A) 57.6(3)

C(4A)-N(1A)-C(5A)-C(6A) 177.9(2) C(1A)-N(1A)-C(5A)-C(6A) 56.5(3)

C(4A)-N(1A)-C(5A)-C(12A) -56.7(3) C(1A)-N(1A)-C(5A)-C(12A) -178.1(2)




C(6A)-C(7A)-C(8A)-C(9A) -1.0(4) C(7A)-C(8A)-C(9A)-C(10A) -1.8(4)

C(7A)-C(8A)-C(9A)-Cl(1A) 176.2(2) C(8A)-C(9A)-C(10A)-C(11A) 3.2(5)

Cl(1A)-C(9A)-C(10A)-C(11A) -174.8(2) C(9A)-C(10A)-C(11A)-C(6A) -1.7(4)



456


C(17A)-C(12A)-C(13A)-C(14A) 0.3(5) C(5A)-C(12A)-C(13A)-C(14A) 178.6(3)


C(14A)-C(15A)-C(16A)-C(17A) -0.5(5) C(15A)-C(16A)-C(17A)-C(12A) -0.3(5)


C(3A)-N(2A)-C(18A)-C(19A) -72.7(3 )C(2A)-N(2A)-C(18A)-C(19A) 167.0(2)

C(20A)-O(1A)-C(19A)-C(18A) 159.0(3) N(2A)-C(18A)-C(19A)-O(1A) -60.1(3)

C(19A)-O(1A)-C(20A)-C(21A) -82.5(4) O(1A)-C(20A)-C(21A)-O(3A) 19.3(5)

O(1A)-C(20A)-C(21A)-O(2A) -161.1(3) C(4B)-N(1B)-C(1B)-C(2B) 50.0(3)

C(5B)-N(1B)-C(1B)-C(2B) 171.3(2) C(3B)-N(2B)-C(2B)-C(1B) 62.5(3)

C(18B)-N(2B)-C(2B)-C(1B) -174.9(2) N(1B)-C(1B)-C(2B)-N(2B) -57.8(3)

C(2B)-N(2B)-C(3B)-C(4B) -63.3(3) C(18B)-N(2B)-C(3B)-C(4B) 173.0(2)

C(1B)-N(1B)-C(4B)-C(3B) -49.4(3) C(5B)-N(1B)-C(4B)-C(3B) -169.4(2)

N(2B)-C(3B)-C(4B)-N(1B) 58.2(3) C(4B)-N(1B)-C(5B)-C(12B) -58.4(3)

C(1B)-N(1B)-C(5B)-C(12B) -179.4(2) C(4B)-N(1B)-C(5B)-C(6B) 174.6(2)

C(1B)-N(1B)-C(5B)-C(6B) 53.6(3) C(12B)-C(5B)-C(6B)-C(7B) -58.2(3)

N(1B)-C(5B)-C(6B)-C(7B) 70.2(3) C(12B)-C(5B)-C(6B)-C(11B) 123.4(3)

N(1B)-C(5B)-C(6B)-C(11B) -108.2(3) C(11B)-C(6B)-C(7B)-C(8B) 3.0(5)

C(5B)-C(6B)-C(7B)-C(8B) -175.3(3) C(6B)-C(7B)-C(8B)-C(9B) -0.7(5)

C(7B)-C(8B)-C(9B)-C(10B) -1.9(5) C(7B)-C(8B)-C(9B)-Cl(1B) 176.1(3)

C(8B)-C(9B)-C(10B)-C(11B) 2.2(6) Cl(1B)-C(9B)-C(10B)-C(11B) -175.9(3)

C(9B)-C(10B)-C(11B)-C(6B) 0.2(6) C(7B)-C(6B)-C(11B)-C(10B) -2.8(5)


N(1B)-C(5B)-C(12B)-C(17B) 159.0(3) C(6B)-C(5B)-C(12B)-C(13B) 103.1(3)

N(1B)-C(5B)-C(12B)-C(13B) -22.3(4) C(17B)-C(12B)-C(13B)-C(14B) -0.8(5)

C(5B)-C(12B)-C(13B)-C(14B) -179.5(3) C(12B)-C(13B)-C(14B)-C(15B) 2.8(5)

C(13B)-C(14B)-C(15B)-C(16B) -2.6(5) C(14B)-C(15B)-C(16B)-C(17B) 0.4(6)


C(5B)-C(12B)-C(17B)-C(16B) 177.4(3) C(3B)-N(2B)-C(18B)-C(19B) -166.4(3)

C(2B)-N(2B)-C(18B)-C(19B) 73.6(3) C(20B)-O(1B)-C(19B)-C(18B) -158.3(3)

N(2B)-C(18B)-C(19B)-O(1B) 61.1(4) C(19B)-O(1B)-C(20B)-C(21B) 84.1(4)

O(1B)-C(20B)-C(21B)-O(2B) -14.5(6) O(1B)-C(20B)-C(21B)-O(3B) 165.5(4)

O(1C)-C(1C)-C(2C)-C(3C) 175.9(3) C(6C)-C(1C)-C(2C)-C(3C) -0.7(4)

O(1C)-C(1C)-C(2C)-N(1C) -0.6(4) C(6C)-C(1C)-C(2C)-N(1C) -177.2(3)

O(2C)-N(1C)-C(2C)-C(3C) 127.6(3) O(3C)-N(1C)-C(2C)-C(3C) -51.8(4)

O(2C)-N(1C)-C(2C)-C(1C) -55.6(4) O(3C)-N(1C)-C(2C)-C(1C) 124.9(3)

C(1C)-C(2C)-C(3C)-C(4C) 0.2(5) N(1C)-C(2C)-C(3C)-C(4C) 176.6(3)

C(2C)-C(3C)-C(4C)-C(5C) -1.0(4) C(2C)-C(3C)-C(4C)-N(2C) -178.7(3)



C(3C)-C(4C)-C(5C)-C(6C) 2.3(4) N(2C)-C(4C)-C(5C)-C(6C) 180.0(3)

C(4C)-C(5C)-C(6C)-C(1C) -2.8(4) C(4C)-C(5C)-C(6C)-N(3C) 178.3(3)

O(1C)-C(1C)-C(6C)-C(5C) -174.3(3) C(2C)-C(1C)-C(6C)-C(5C) 2.0(4)

O(1C)-C(1C)-C(6C)-N(3C) 4.5(4) C(2C)-C(1C)-C(6C)-N(3C) -179.2(2)



O(1D)-C(1D)-C(2D)-C(3D) 176.3(3) C(6D)-C(1D)-C(2D)-C(3D) -3.6(4)

O(1D)-C(1D)-C(2D)-N(1D) -3.5(4) C(6D)-C(1D)-C(2D)-N(1D) 176.7(3)

O(3D)-N(1D)-C(2D)-C(3D) -34.6(4) O(2D)-N(1D)-C(2D)-C(3D) 140.2(3)

O(3D)-N(1D)-C(2D)-C(1D) 145.1(3) O(2D)-N(1D)-C(2D)-C(1D) -40.0(4)

C(1D)-C(2D)-C(3D)-C(4D) 4.6(4) N(1D)-C(2D)-C(3D)-C(4D) -175.7(3)

C(2D)-C(3D)-C(4D)-C(5D) -1.7(4) C(2D)-C(3D)-C(4D)-N(2D) 179.5(2)


457


C(3D)-C(4D)-C(5D)-C(6D) -1.7(4) N(2D)-C(4D)-C(5D)-C(6D) 177.0(2)

C(4D)-C(5D)-C(6D)-C(1D) 2.6(4) C(4D)-C(5D)-C(6D)-N(3D) -179.1(2)

O(1D)-C(1D)-C(6D)-C(5D) -179.9(2) C(2D)-C(1D)-C(6D)-C(5D) -0.1(4)

O(1D)-C(1D)-C(6D)-N(3D) 1.8(4) C(2D)-C(1D)-C(6D)-N(3D) -178.4(2)



O(2E)-N(1E)-C(2E)-C(3E) -140.4(3) O(3E)-N(1E)-C(2E)-C(3E) 37.7(4)

O(2E)-N(1E)-C(2E)-C(1E) 39.0(4) O(3E)-N(1E)-C(2E)-C(1E) -143.0(3)

O(1E)-C(1E)-C(2E)-C(3E) -175.0(3) C(6E)-C(1E)-C(2E)-C(3E) 3.3(4)

O(1E)-C(1E)-C(2E)-N(1E) 5.7(4) C(6E)-C(1E)-C(2E)-N(1E) -175.9(3)

N(1E)-C(2E)-C(3E)-C(4E) 176.0(3) C(1E)-C(2E)-C(3E)-C(4E) -3.3(4)

C(2E)-C(3E)-C(4E)-C(5E) 0.8(4) C(2E)-C(3E)-C(4E)-N(2E) 179.8(2)



C(3E)-C(4E)-C(5E)-C(6E) 1.3(4) N(2E)-C(4E)-C(5E)-C(6E) -177.7(2)

C(4E)-C(5E)-C(6E)-C(1E) -1.1(4) C(4E)-C(5E)-C(6E)-N(3E) -179.7(2)

O(1E)-C(1E)-C(6E)-C(5E) 177.2(3) C(2E)-C(1E)-C(6E)-C(5E) -1.1(4)

O(1E)-C(1E)-C(6E)-N(3E) -4.2(4) C(2E)-C(1E)-C(6E)-N(3E) 177.5(2)



O(1F)-C(1F)-C(2F)-C(3F) -173.2(3) C(6F)-C(1F)-C(2F)-C(3F) 5.0(4)

O(1F)-C(1F)-C(2F)-N(1F) 5.8(4) C(6F)-C(1F)-C(2F)-N(1F) -175.9(2)

O(3F)-N(1F)-C(2F)-C(3F) 57.0(4) O(2F)-N(1F)-C(2F)-C(3F) -123.1(3)

O(3F)-N(1F)-C(2F)-C(1F) -122.1(3) O(2F)-N(1F)-C(2F)-C(1F) 57.7(4)

C(1F)-C(2F)-C(3F)-C(4F) -3.7(4) N(1F)-C(2F)-C(3F)-C(4F) 177.3(3)

C(2F)-C(3F)-C(4F)-C(5F) 0.8(4) C(2F)-C(3F)-C(4F)-N(2F) -178.2(2)



C(3F)-C(4F)-C(5F)-C(6F) 0.1(4) N(2F)-C(4F)-C(5F)-C(6F) 179.1(2)

C(4F)-C(5F)-C(6F)-C(1F) 1.8(4) C(4F)-C(5F)-C(6F)-N(3F) -177.8(3)

O(1F)-C(1F)-C(6F)-C(5F) 174.2(3) C(2F)-C(1F)-C(6F)-C(5F) -4.0(4)

O(1F)-C(1F)-C(6F)-N(3F) -6.2(4) C(2F)-C(1F)-C(6F)-N(3F) 175.6(2)




D-H∙∙∙A d(D-H) d(H∙∙∙A) d(D∙∙∙A) <(DHA)

O(2A)-H(2AD)...O(2B) 0.84 1.80 2.638(4) 179.6

N(1A)-H(1AC)...O(1D) 0.93 1.83 2.682(3) 151.6

N(1A)-H(1AC)...O(7D) 0.93 2.63 3.301(3) 129.2

N(2A)-H(2AC)...O(1C) 0.93 1.89 2.765(3) 155.0

N(2A)-H(2AC)...O(7C) 0.93 2.46 2.990(3) 116.3

O(3B)-H(3BC)...O(3A) 0.84 1.76 2.601(4) 179.9

N(1B)-H(1BC)...O(1E) 0.93 1.85 2.678(3) 147.4

N(1B)-H(1BC)...O(7E) 0.93 2.52 3.193(3) 129.9

N(2B)-H(2BC)...O(1F) 0.93 1.91 2.764(3) 152.6

N(2B)-H(2BC)...O(7F) 0.93 2.57 3.078(4) 115.0

C19(B)-H19(C)...Cg5i 0.99 2.95 3.792(4) 144.0

Symmetry codes: (i) x + 1; y; z.

458

Table 4.44 - Cg···Cg π stacking interactions (Å)

Cg8 is the centroid of ring C1D–C6D and Cg9 is the centroid of the ring C1E–C6E.

CgX···CgY CgX···Perp CgY···Perp

Cg8···Cg9i 3.7419 (14) 3.2668 (9) -3.3033 (9)

Symmetry code: (i) x, y,-1+z.

The molecular structure of the title compound with N—H···O intermolecular

hydrogen bonds is shown in Fig. 4.23.



indicate strong and weak N—H···O intermolecular hydrogen bonds

In the crystal structure of the title compound, the six-membered piperazine

groups (N1A/C1A/C2A/N2A/C3A/C4A & N1B/C1B/C2B/N2B/C3B/C4B) in the

levocetirizinium cation are protonated at both N atoms (Fig. 4.22) and adopt slightly

distorted chair conformations with puckering parameters Q, θ and φ of 0.591 (3)A%

& 0.583 (3) Å, 171.6 (3)° & 170.8 (3)°, and 353.0 (17)° & 358.2 (19)°, for molecules

A & B respectively (Figs. 4.22 & 4.23). For an ideal chair θ has a value of 0 or 180°.

Bond distances (Allen et al., 1987) and angles are in normal ranges. R21(6) graph-set

motifs are formed between piperazine N1A—H1AC and N2A—H2AC groups and the

picrate anions labeled D and C (Fig. 4.22) and piperazine N1B—H1BC and N2B—

H2BC groups and the picrate anions labeled E and F through bifurcated N—H···O

hydrogen bonds. The acetyl end groups form an R22(8) hydrogen bonded motif with

adjacent cations (Fig. 4.24). The dihedral angle between the mean planes of the anion

benzene ring pairs is 31.9 (2) Å (C—D) and 37.9 (6) Å (E—F), respectively.

459

Fig. 4.24 - Molecular structure of adjacent cations from the title compound

showing the acetyl end groups forming R22(8) hydrogen bonded motif.


460


Fig. 4.27 - Packing diagram of the title compound viewed down the b axis.

Dashed lines indicate strong and weak intermolecular N—H···O and

O—H···O hydrogen bond interactions creating a 3-D supramolecular

structure.

461


Packing of the molecules along a, b and c axes are shown in Figs. 4.25,

4.26/4.27 and 4.28 respectively. Fig. 4.27 clearly shows the N—H···O and O—H···O

hydrogen bond interactions. In the title compound (XXIII), the selected bond lengths

(Å), bond angles (°) and torsion angles (°) respectively are:- O1A—C20A = 1.413 (4),

O1A—C19A = 1.425 (4), O2A—C21A = 1.306 (4), N1A—C4A = 1.502 (3), N1A—

C1A = 1.512 (3), N1A—C5A = 1.526 (3); C20A—O1A—C19A = 114.4 (3), C4A—

N1A—C1A = 110.86 (19), C4A—N1A—C5A = 108.93 (19), C1A—N1A—C5A =

109.52 (19), O1A—C19A—C18A = 108.0 (3), C19A—C18A—N2A = 111.9 (2);

C4A—N1A—C1A—C2A = 51.3 (3), C5A—N1A—C1A—C2A = 171.5 (2), C18A—

N2A—C2A—C1A = −172.3 (2), N1A—C1A—C2A—N2A = −59.0 (3), C4A—

N1A—C5A—C6A = 177.9 (2), C11A—C6A—C7A—C8A = 2.4 (4), C7A—C8A—

C9A—C10A = −1.8 (4), C17A—C12A—C13A—C14A = 0.3 (5). These values agree

well with the reported similar structures.

462

In the title compound (XXIII), the mean plane of the two o-NO2 groups in the

two picrate anions are twisted by 15.8 (6)°, 53.7 (3)Å (ring C), 25.9 (9) Å, 38.5 (1)Å

(ring D), 24.5 (0) Å, 38.7 (2) Å (ring E) and 10.3 (3) Å, 56.9 (9) Å (ring F) with

respect to the mean planes of the 6-membered benzene rings. The p-NO2 groups in

both picrate anions are nearly in the plane of the ring (torsion angles

O4C/N2C/C4C/C3C = -8.8 (4)°; O4D/N2D/C4D/C3D = -175.8 (2)°; O4E/N2E/C4E/C3E

= 2.6 (4)°; O4F/N2F/C4F/C3F = 3.4 (4)°;). An extensive array of strong and weak N—

H···O and strong O—H···O intermolecular hydrogen bonds and weak π-ring (Table

4.43) and π-π (Table 4.44) stacking interactions dominate crystal packing in the unit

cell creating a 3-D supramolecular structure (Fig. 4.27). Classic hydrogen bonds

found for the present structure.

* * * * *

463

Section 4.6

Crystal structure studies of lomefloxacinium picrate

Abstract

In the cation of the title compound [systematic name: (RS)-4-(3-carboxy-1-

ethyl-6,8-difluoro-4-oxo-1,4-dihydroquinolin-7-yl)-2-methyl piperazin-1-ium 2,4,6-

trinitrophenolate], C17H20-F2N3O3+.C6H2N3O7

-, the piperazine ring adopts a slightly

distorted chair conformation and contains a protonated N atom. An intramolecular

O—H···O hydrogen bond occurs in the cation. The dihedral angles between the mean

planes of the six-atom piperazine ring and the ten-atom fused ring system is 43.3 (5)°.

The picrate anion interacts with the protonated N atom of an adjacent cation through a

bifurcated N—H···(O,O) three-center hydrogen bond. Strong N—H···O hydrogen

bonds in concert with weak π–π stacking interactions [centroid–centroid distance =

3.6460 (14) Å] dominate the crystal packing, creating a two-dimensional network

structure along [011]. Classical hydrogen bonds found for the present structure.

The title compound, crystallizes in a triclinic space group P ī with a =

10.9314(4) Å; b = 11.6748(4) Å; c = 12.0530(4) Å; α = 92.969(3)°; β = 115.555(3)°; γ

= 109.852(3)°; V = 1269.14(8) Å3; Z = 2; D cal = 1.519 Mg/m

3 at T = 123(2) K. The

structure was solved by direct methods and refined by full-matrix least-squares

procedures to final R1 = 0.0627 and wR2 = 0.1760 using 5002 reflections.

Introduction

Lomefloxacin hydrochloride is a fluoroquinolone antibiotic, used to treat

bacterial infections including bronchitis and urinary tract infections. It is also used to

prevent urinary tract infections prior to surgery. Lomefloxacin, chemically, (RS)-1-

ethyl-6,8-difluoro-7-(3-methylpiperazin-1-yl)-4-oxo-quinoline-3-carboxylic acid is

associated with phototoxicity and central nervous system adverse effects (Rubinstein

et al., 2001). Recently, the crystal structures of propiverine picrate (Jasinski et al.,

2010), imatinibium dipicrate (Jasinski et al., 2010a) and chlorimipraminium picrate

(Jasinski et al., 2010b) have been reported.

464

In continuation of our work on picrates of biologically active compounds, the

paper reports the crystal structure of (XXIV), C23H22O10N6F2, obtained by the

interaction of picric acid and lomefloxacin. The synthesis and structure of (XXIV) are

reported in this section.

(XXIV)


Experimental

Lomefloxacin (3.87 g, 0.01 mol) of picric acid (2.52 g, 0.01 mol) was

dissolved in 15 ml of dimethyl formamide. The solution was stirred for 15 min over a

heating magnetic stirrer at 335 K. The resulting solution was kept aside at room

temperature. X-ray quality crystals were grown from slow evaporation of dimethyl

formamide solution (m.p.: 489 – 491 K).


N

F

F

N

NH2

CH3

O

CHO

O

O

NO2

NO2O2NCH3

N

F

F

N

NH

CH3

O

CHO

O

HO

NO2

NO2O2NCH3

+

DMF

Reaction scheme

465

Refinement

The O atoms on one of the o-nitrate groups in the picrate anion are disordered

[occupancy O6A and O7A = 0.762 (4); O6B and O7B = 0.238 (4)]. The N3B–O6A

and N3B–O6B dstances were fixed at 1.23Å. The O6A–O7A and O6B–O7B angular

distances were fixed at 2.15Å. All of the H atoms were placed in their calculated

positions and then refined using the riding model with Atom—H lengths of 0.95Å

(CH), 0.99Å (CH2), 0.98Å (CH3), 0.92Å (NH), or 0.84 (OH). Isotropic displacement

parameters for these atoms were set to 1.20 times (NH), 1.45 (OH), 1.19-1.20 (CH,

CH2) or 1.49 (CH3) times Ueq of the parent atom.

Special details










2 > σ(F

2) is used only for




Computing details


PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to



software used to prepare material for publication: SHELXTL.

466








are listed in Tables 4.51 and 4.52. The torsion angles are presented in Table 4.53.

Table 4.54 gives hydrogen-bond geometry and Cg···Cg π stacking interactions are

given in Table 4.55. Fig. 4.29 shows the molecular structure with 50% probability

displacement ellipsoids.

Fig. 4.29 - The molecular structure of the title compound showing the atom

labeling scheme and 50% probability displacement ellipsoids. Dashed

lines indicate a intramolecular O—H···O hydrogen bond in the cation

and a bifurcated N—H···(O,O) intermolecular three-centered hydrogen

bond formed between the protonated N atom from the

lomefloxacinium cation and the picrate anion. In the picrate anion only

the predominate disordered O6A and O7A (0.762 (4)) atoms are

displayed.

467


Empirical formula C23H22F2N6O10




Crystal system Triclinic

Space group P ī

Unit cell dimensions a = 10.9314(4) Å α = 92.969(3)°

b = 11.6748(4) Å β = 115.555(3)°

c = 12.0530(4) Å γ = 109.852(3)°

Volume 1269.14(8) Å3

Z 2



F(000) 600



Index ranges -13<=h<=13, -14<=k<=14, -15<=l<=11












468




Atoms x y z U(eq)

F(1) 6040(2) 5155(1) 1489(2) 71(1)

F(2) 5634(2) 2135(1) 3865(1) 63(1)

O(1) 1692(3) -2598(2) -1642(2) 87(1)

O(2) 1664(2) -1194(2) -2795(2) 77(1)

O(3) 3098(2) 1105(2) -1745(2) 68(1)

N(1) 4327(2) 177(2) 1687(2) 43(1)

N(2) 6695(2) 4628(2) 3820(2) 54(1)

N(3) 8631(2) 6765(2) 5829(2) 50(1)

C(1) 3494(2) -691(2) 592(2) 48(1)

C(2) 3035(2) -440(2) -570(2) 50(1)

C(3) 3466(2) 821(2) -691(2) 49(1)

C(4) 4355(2) 1778(2) 492(2) 42(1)

C(5) 4789(3) 3043(2) 450(2) 48(1)

C(6) 5557(3) 3938(2) 1535(2) 49(1)

C(7) 5903(2) 3680(2) 2737(2) 44(1)

C(8) 5437(2) 2416(2) 2746(2) 43(1)

C(9) 4724(2) 1442(2) 1660(2) 39(1)

C(10) 6252(3) 5651(2) 3948(3) 63(1)

C(11) 7563(3) 6886(2) 4583(2) 59(1)

C(12) 7180(5) 7966(3) 4768(3) 87(1)

C(13) 9053(3) 5704(2) 5683(2) 57(1)

C(14) 7716(3) 4504(2) 5034(2) 60(1)

C(15) 4739(3) -308(2) 2859(2) 55(1)

C(16) 3578(4) -604(3) 3273(3) 72(1)

C(17) 2083(3) -1517(3) -1693(3) 64(1)

O(1B) 7432(2) 6072(2) 7371(2) 62(1)

O(2B) 9066(3) 8637(2) 7905(2) 76(1)

O(3B) 8490(2) 9471(2) 9140(2) 57(1)

O(4B) 10088(4) 8184(3) 13143(2) 98(1)

O(5B) 9633(3) 6233(3) 13096(2) 92(1)

O(6A) 6326(4) 3355(3) 8579(4) 95(1)

O(7A) 7897(5) 3879(3) 7883(5) 112(1)

O(6B) 6422(16) 3618(10) 7938(15) 95(1)

O(7B) 8327(16) 3524(9) 9132(13) 112(1)

N(1B) 8724(2) 8621(2) 8747(2) 47(1)

N(2B) 9639(3) 7107(3) 12575(2) 69(1)

N(3B) 7444(3) 4116(2) 8599(3) 68(1)

C(1B) 7999(3) 6332(2) 8550(2) 48(1)

C(2B) 8634(2) 7566(2) 9345(2) 45(1)

C(3B) 9122(3) 7818(2) 10622(2) 48(1)

C(4B) 9080(3) 6845(3) 11223(2) 55(1)

C(5B) 8520(3) 5619(2) 10551(3) 59(1)

C(6B) 8021(3) 5400(2) 9288(3) 54(1)


469


3) for

the non-hydrogen atoms

Atoms U

11 U

22 U

33 U

23 U

13 U

12

F(1) 79(1) 38(1) 66(1) 18(1) 17(1) 13(1)

F(2) 90(1) 40(1) 36(1) 5(1) 20(1) 14(1)

O(1) 78(1) 51(1) 77(2) -23(1) 8(1) 11(1)

O(2) 64(1) 82(1) 46(1) -16(1) 13(1) 8(1)

O(3) 68(1) 75(1) 36(1) 4(1) 14(1) 17(1)

N(1) 43(1) 33(1) 41(1) 1(1) 11(1) 14(1)

N(2) 54(1) 34(1) 44(1) -4(1) 1(1) 19(1)

N(3) 53(1) 37(1) 40(1) -4(1) 10(1) 14(1)

C(1) 42(1) 35(1) 53(1) -4(1) 14(1) 13(1)

C(2) 39(1) 48(1) 44(1) -9(1) 11(1) 13(1)

C(3) 39(1) 57(1) 37(1) -1(1) 12(1) 16(1)

C(4) 37(1) 42(1) 36(1) 2(1) 11(1) 14(1)

C(5) 47(1) 48(1) 40(1) 13(1) 14(1) 18(1)

C(6) 46(1) 34(1) 51(1) 12(1) 14(1) 12(1)

C(7) 39(1) 35(1) 40(1) 1(1) 7(1) 12(1)

C(8) 44(1) 37(1) 33(1) 4(1) 10(1) 12(1)

C(9) 37(1) 34(1) 38(1) 3(1) 12(1) 13(1)

C(10) 56(1) 45(1) 60(2) -4(1) 5(1) 23(1)

C(11) 68(2) 42(1) 49(1) 3(1) 13(1) 23(1)

C(12) 111(3) 55(2) 71(2) 1(1) 15(2) 46(2)

C(13) 56(1) 50(1) 44(1) -3(1) 6(1) 24(1)

C(14) 65(2) 41(1) 46(1) -1(1) 2(1) 23(1)

C(15) 64(2) 36(1) 51(1) 11(1) 15(1) 21(1)

C(16) 82(2) 59(2) 63(2) 19(1) 32(2) 17(2)

C(17) 46(1) 65(2) 53(2) -16(1) 12(1) 13(1)

O(1B) 68(1) 49(1) 48(1) 1(1) 21(1) 9(1)

O(2B) 128(2) 53(1) 66(1) 21(1) 62(1) 36(1)

O(3B) 55(1) 43(1) 72(1) 12(1) 28(1) 25(1)

O(4B) 128(2) 101(2) 54(1) 13(1) 41(1) 38(2)

O(5B) 121(2) 118(2) 74(1) 57(2) 55(2) 73(2)

O(6A) 103(2) 45(2) 135(4) 11(2) 74(2) 6(2)

O(7A) 158(4) 63(2) 145(3) 6(2) 102(3) 40(2)

O(6B) 103(2) 45(2) 135(4) 11(2) 74(2) 6(2)

O(7B) 158(4) 63(2) 145(3) 6(2) 102(3) 40(2)

N(1B) 49(1) 37(1) 45(1) 7(1) 16(1) 15(1)

N(2B) 75(2) 87(2) 56(1) 26(1) 35(1) 40(1)

N(3B) 72(2) 35(1) 91(2) 11(1) 37(2) 17(1)

C(1B) 46(1) 39(1) 54(1) 8(1) 23(1) 14(1)

C(2B) 46(1) 39(1) 48(1) 12(1) 21(1) 17(1)

C(3B) 48(1) 45(1) 50(1) 8(1) 23(1) 17(1)

C(4B) 58(1) 62(2) 51(1) 21(1) 29(1) 28(1)

C(5B) 68(2) 51(1) 73(2) 29(1) 42(1) 29(1)

C(6B) 56(1) 40(1) 66(2) 13(1) 30(1) 18(1)


2a*

2U

11+ ... + 2 h k a* b* U

12]

470



F(1)-C(6) 1.350(3) F(2)-C(8) 1.348(3)

O(1)-C(17) 1.201(4) O(2)-C(17) 1.327(4)

O(3)-C(3) 1.257(3) N(1)-C(1) 1.340(3)

N(1)-C(9) 1.396(3) N(1)-C(15) 1.492(3)

N(2)-C(7) 1.381(3) N(2)-C(10) 1.457(3)

N(2)-C(14) 1.459(3) N(3)-C(13) 1.489(3)

N(3)-C(11) 1.503(3) C(1)-C(2) 1.355(4)

C(2)-C(3) 1.422(4) C(2)-C(17) 1.488(3)

C(3)-C(4) 1.458(3) C(4)-C(5) 1.401(3)

C(4)-C(9) 1.405(3) C(5)-C(6) 1.349(3)

C(6)-C(7) 1.408(3) C(7)-C(8) 1.390(3)

C(8)-C(9) 1.406(3) C(10)-C(11) 1.502(4)

C(11)-C(12) 1.492(4) C(13)-C(14) 1.489(4)

C(15)-C(16) 1.498(4) O(1B)-C(1B) 1.250(3)

O(2B)-N(1B) 1.222(3) O(3B)-N(1B) 1.226(2)

O(4B)-N(2B) 1.223(4) O(5B)-N(2B) 1.225(3)

O(6A)-N(3B) 1.232(5) O(7A)-N(3B) 1.226(4)

O(6B)-N(3B) 0.981(14) O(7B)-N(3B) 1.336(14)

N(1B)-C(2B) 1.455(3) N(2B)-C(4B) 1.444(4)

N(3B)-C(6B) 1.454(3) C(1B)-C(2B) 1.442(3)

C(1B)-C(6B) 1.442(3) C(2B)-C(3B) 1.371(3)

C(3B)-C(4B) 1.378(3) C(4B)-C(5B) 1.391(4)

C(5B)-C(6B) 1.352(4)



C(1)-N(1)-C(9) 119.08(19) C(1)-N(1)-C(15) 115.88(19)

C(9)-N(1)-C(15) 125.03(18) C(7)-N(2)-C(10) 121.84(19)

C(7)-N(2)-C(14) 122.76(18) C(10)-N(2)-C(14) 112.8(2)

C(13)-N(3)-C(11) 112.21(18) N(1)-C(1)-C(2) 124.9(2)

C(1)-C(2)-C(3) 120.0(2) C(1)-C(2)-C(17) 118.0(2)

C(3)-C(2)-C(17) 122.0(2) O(3)-C(3)-C(2) 122.7(2)

O(3)-C(3)-C(4) 121.6(2) C(2)-C(3)-C(4) 115.8(2)

C(5)-C(4)-C(9) 120.05(19) C(5)-C(4)-C(3) 119.2(2)

C(9)-C(4)-C(3) 120.7(2) C(6)-C(5)-C(4) 119.8(2)

C(5)-C(6)-F(1) 119.3(2) C(5)-C(6)-C(7) 123.6(2)

F(1)-C(6)-C(7) 117.1(2) N(2)-C(7)-C(8) 123.3(2)

N(2)-C(7)-C(6) 121.5(2) C(8)-C(7)-C(6) 115.20(19)

F(2)-C(8)-C(7) 116.59(18) F(2)-C(8)-C(9) 119.43(19)

C(7)-C(8)-C(9) 123.9(2) N(1)-C(9)-C(4) 119.30(18)

N(1)-C(9)-C(8) 123.52(19) C(4)-C(9)-C(8) 117.15(19)

N(2)-C(10)-C(11) 111.7(2) C(12)-C(11)-C(10) 114.1(3)

C(12)-C(11)-N(3) 110.6(2) C(10)-C(11)-N(3) 108.0(2)

N(3)-C(13)-C(14) 110.7(2) N(2)-C(14)-C(13) 109.2(2)

N(1)-C(15)-C(16) 112.5(2) H(16A)-C(16)-H(16C) 109.5

H(16B)-C(16)-H(16C) 109.5 O(1)-C(17)-O(2) 121.2(2)

471

O(1)-C(17)-C(2) 124.5(3) O(2)-C(17)-C(2) 114.3(3)

O(2B)-N(1B)-O(3B) 123.1(2) O(2B)-N(1B)-C(2B) 118.87(19)

O(3B)-N(1B)-C(2B) 118.0(2) O(4B)-N(2B)-O(5B) 123.2(3)

O(4B)-N(2B)-C(4B) 118.6(3) O(5B)-N(2B)-C(4B) 118.2(3)

O(6B)-N(3B)-O(7A) 89.8(8) O(6B)-N(3B)-O(6A) 45.1(8)

O(7A)-N(3B)-O(6A) 121.7(3) O(6B)-N(3B)-O(7B) 118.6(9)

O(7A)-N(3B)-O(7B) 71.4(5) O(6A)-N(3B)-O(7B) 97.0(6)

O(6B)-N(3B)-C(6B) 126.1(8) O(7A)-N(3B)-C(6B) 119.5(3)

O(6A)-N(3B)-C(6B) 117.4(3) O(7B)-N(3B)-C(6B) 113.6(6)

O(1B)-C(1B)-C(2B) 125.7(2) O(1B)-C(1B)-C(6B) 123.3(2)

C(2B)-C(1B)-C(6B) 110.9(2) C(3B)-C(2B)-C(1B) 124.8(2)

C(3B)-C(2B)-N(1B) 117.2(2) C(1B)-C(2B)-N(1B) 117.9(2)

C(2B)-C(3B)-C(4B) 118.8(2) C(2B)-C(3B)-H(3BA) 120.6

C(4B)-C(3B)-H(3BA) 120.6 C(3B)-C(4B)-C(5B) 121.2(2)

C(3B)-C(4B)-N(2B) 119.2(2) C(5B)-C(4B)-N(2B) 119.6(2)

C(6B)-C(5B)-C(4B) 118.5(2) C(6B)-C(5B)-H(5BA) 120.8

C(4B)-C(5B)-H(5BA) 120.8 C(5B)-C(6B)-C(1B) 125.7(2)

C(5B)-C(6B)-N(3B) 118.0(2) C(1B)-C(6B)-N(3B) 116.3(2)

C(11)-C(12)-C(13) 120.1(2) C(12)-C(13)-C(8) 120.0(2)




Atoms x y z U(eq)

H(2) 1981 -410 -2669 115

H(3A) 9469 7498 6209 60

H(3B) 8206 6647 6351 60

H(1A) 3204 -1545 634 58

H(5A) 4543 3271 -339 58

H(10A) 5719 5485 4448 75

H(10B) 5564 5692 3099 75

H(11A) 8060 7053 4044 71

H(12A) 8084 8738 5172 130

H(12B) 6708 7831 5309 130

H(12C) 6496 8039 3946 130

H(13A) 9725 5640 6526 68

H(13B) 9589 5863 5184 68

H(14A) 8008 3816 4898 72

H(14B) 7227 4302 5566 72

H(15A) 5684 325 3547 65

H(15B) 4895 -1075 2704 65

H(16A) 3837 -1017 3978 108

H(16B) 2617 -1163 2566 108

H(16C) 3522 173 3547 108

H(3BA) 9483 8650 11084 58

H(5BA) 8489 4951 10971 71

472



O(2)-H(2) 0.8400 N(3)-H(3A) 0.9200

N(3)-H(3B) 0.9200 C(1)-H(1A) 0.9500

C(5)-H(5A) 0.9500 C(10)-H(10A) 0.9900

C(10)-H(10B) 0.9900 C(11)-H(11A) 1.0000

C(12)-H(12A) 0.9800 C(12)-H(12B) 0.9800

C(12)-H(12C) 0.9800 C(13)-H(13A) 0.9900

C(13)-H(13B) 0.9900 C(14)-H(14A) 0.9900

C(14)-H(14B) 0.9900 C(15)-H(15A) 0.9900

C(15)-H(15B) 0.9900 C(16)-H(16A) 0.9800

C(16)-H(16B) 0.9800 C(16)-H(16C) 0.9800

C(5B)-H(5BA) 0.9500 C(3B)-H(3BA) 0.9500

Table 4.52- Bond angles [º] for the hydrogen atoms


C(17)-O(2)-H(2) 109.5 C(13)-N(3)-H(3A) 109.2

C(11)-N(3)-H(3A) 109.2 C(13)-N(3)-H(3B) 109.2

C(11)-N(3)-H(3B) 109.2 H(3A)-N(3)-H(3B) 107.9

N(1)-C(1)-H(1A) 117.6 C(2)-C(1)-H(1A) 117.6

C(6)-C(5)-H(5A) 120.1 C(4)-C(5)-H(5A) 120.1

N(2)-C(10)-H(10A) 109.3 C(11)-C(10)-H(10A) 109.3

N(2)-C(10)-H(10B) 109.3 C(11)-C(10)-H(10B) 109.3

H(10A)-C(10)-H(10B) 107.9 C(12)-C(11)-H(11A) 108.0

C(10)-C(11)-H(11A) 108.0 N(3)-C(11)-H(11A) 108.0

C(11)-C(12)-H(12A) 109.5 C(11)-C(12)-H(12B) 109.5

H(12A)-C(12)-H(12B) 109.5 C(11)-C(12)-H(12C) 109.5

H(12A)-C(12)-H(12C) 109.5 H(12B)-C(12)-H(12C) 109.5

N(3)-C(13)-H(13A) 109.5 C(14)-C(13)-H(13A) 109.5

N(3)-C(13)-H(13B) 109.5 C(14)-C(13)-H(13B) 109.5

H(13A)-C(13)-H(13B) 108.1 N(2)-C(14)-H(14A) 109.8

C(13)-C(14)-H(14A) 109.8 N(2)-C(14)-H(14B) 109.8

C(13)-C(14)-H(14B) 109.8 H(14A)-C(14)-H(14B) 108.3

N(1)-C(15)-H(15A) 109.1 C(16)-C(15)-H(15A) 109.1

N(1)-C(15)-H(15B) 109.1 C(16)-C(15)-H(15B) 109.1

H(15A)-C(15)-H(15B) 107.8 C(15)-C(16)-H(16A) 109.5

C(15)-C(16)-H(16B) 109.5 H(16A)-C(16)-H(16B) 109.5

C(15)-C(16)-H(16C) 109.5



C(9)-N(1)-C(1)-C(2) 2.5(3) C(15)-N(1)-C(1)-C(2) -178.4(2)

N(1)-C(1)-C(2)-C(3) 1.5(4) N(1)-C(1)-C(2)-C(17) -178.6(2)

C(1)-C(2)-C(3)-O(3) 178.5(2) C(17)-C(2)-C(3)-O(3) -1.4(4)

C(1)-C(2)-C(3)-C(4) -2.3(3) C(17)-C(2)-C(3)-C(4) 177.8(2)

O(3)-C(3)-C(4)-C(5) 1.0(4) C(2)-C(3)-C(4)-C(5) -178.3(2)

O(3)-C(3)-C(4)-C(9) 178.4(2) C(2)-C(3)-C(4)-C(9) -0.9(3)

C(9)-C(4)-C(5)-C(6) -0.3(4) C(3)-C(4)-C(5)-C(6) 177.2(2)

473

C(4)-C(5)-C(6)-F(1) 176.4(2) C(4)-C(5)-C(6)-C(7) -3.2(4)

C(10)-N(2)-C(7)-C(8) -129.6(3) C(14)-N(2)-C(7)-C(8) 30.8(4)

C(10)-N(2)-C(7)-C(6) 52.7(4) C(14)-N(2)-C(7)-C(6) -146.9(3)

C(5)-C(6)-C(7)-N(2) 179.9(2) F(1)-C(6)-C(7)-N(2) 0.3(4)

C(5)-C(6)-C(7)-C(8) 2.1(4) F(1)-C(6)-C(7)-C(8) -177.6(2)

N(2)-C(7)-C(8)-F(2) 7.9(3) C(6)-C(7)-C(8)-F(2) -174.3(2)

N(2)-C(7)-C(8)-C(9) -175.2(2) C(6)-C(7)-C(8)-C(9) 2.6(3)

C(1)-N(1)-C(9)-C(4) -5.6(3) C(15)-N(1)-C(9)-C(4) 175.4(2)

C(1)-N(1)-C(9)-C(8) 172.0(2) C(15)-N(1)-C(9)-C(8) -7.0(3)

C(5)-C(4)-C(9)-N(1) -177.8(2) C(3)-C(4)-C(9)-N(1) 4.8(3)

C(5)-C(4)-C(9)-C(8) 4.5(3) C(3)-C(4)-C(9)-C(8) -172.9(2)

F(2)-C(8)-C(9)-N(1) -6.6(3) C(7)-C(8)-C(9)-N(1) 176.7(2)

F(2)-C(8)-C(9)-C(4) 171.0(2) C(7)-C(8)-C(9)-C(4) -5.7(3)

C(7)-N(2)-C(10)-C(11) -139.0(3) C(14)-N(2)-C(10)-C(11) 58.8(3)

N(2)-C(10)-C(11)-C(12) -178.6(3) N(2)-C(10)-C(11)-N(3) -55.2(3)

C(13)-N(3)-C(11)-C(12) -179.4(3) C(13)-N(3)-C(11)-C(10) 55.1(3)

C(11)-N(3)-C(13)-C(14) -57.1(3) C(7)-N(2)-C(14)-C(13) 140.2(3)

C(10)-N(2)-C(14)-C(13) -57.8(3) N(3)-C(13)-C(14)-N(2) 56.2(3)

C(1)-N(1)-C(15)-C(16) -86.1(3) C(9)-N(1)-C(15)-C(16) 93.0(3)

C(1)-C(2)-C(17)-O(1) -0.1(4) C(3)-C(2)-C(17)-O(1) 179.8(3)

C(1)-C(2)-C(17)-O(2) 179.1(2) C(3)-C(2)-C(17)-O(2) -1.0(4)

O(1B)-C(1B)-C(2B)-C(3B) 173.4(2) C(6B)-C(1B)-C(2B)-C(3B) -3.2(3)

O(1B)-C(1B)-C(2B)-N(1B) -4.6(4) C(6B)-C(1B)-C(2B)-N(1B) 178.8(2)



C(1B)-C(2B)-C(3B)-C(4B) 3.2(4) N(1B)-C(2B)-C(3B)-C(4B) -178.7(2)

C(2B)-C(3B)-C(4B)-C(5B) -1.6(4) C(2B)-C(3B)-C(4B)-N(2B) 177.9(2)



C(3B)-C(4B)-C(5B)-C(6B) 0.3(4) N(2B)-C(4B)-C(5B)-C(6B) -179.1(2)

C(4B)-C(5B)-C(6B)-C(1B) -0.6(4) C(4B)-C(5B)-C(6B)-N(3B) 179.8(2)

O(1B)-C(1B)-C(6B)-C(5B) -174.9(3) C(2B)-C(1B)-C(6B)-C(5B) 1.9(4)


O(6B)-N(3B)-C(6B)-C(5B) 116.5(11) O(7A)-N(3B)-C(6B)-C(5B) -129.5(4)

O(6A)-N(3B)-C(6B)-C(5B) 63.7(4) O(7B)-N(3B)-C(6B)-C(5B) -48.4(6)

O(6B)-N(3B)-C(6B)-C(1B) -63.2(11) O(7A)-N(3B)-C(6B)-C(1B) 50.8(4)

O(6A)-N(3B)-C(6B)-C(1B) -116.0(4) O(7B)-N(3B)-C(6B)-C(1B) 132.0(6)

Table 4.54 – Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A

O2—H2···O3 0.84 1.74 2.520 (3) 153

N3—H3A···O2i 0.92 2.09 2.984 (3) 164

N3—H3B···O1B 0.92 1.81 2.714 (3) 166

N3—H3B···O2B 0.92 2.52 2.993 (3) 113

Symmetry codes: (i) x+1, y+1, z+1.

474

Table 4.55 – Cg···Cg π stacking interactions

Cg1 is the centroid of ring N1/C1/C2/C3/C4/C9; [Symmetry code: (i) 1-x, -y, -z]

CgI···CgJ Cg···Cg (Å) CgI Perp (Å) Cgj Perp (Å) Slippage (Å)

Cg1···Cg1i 3.6460 (14) 3.3385 (10) 3.3385 (10) 1.46 (6



475


Packing of the molecules along a, b and c axes are shown in Figures 4.30,

4.31 and 4.32 respectively. In the crystal structure of the title compound, there is one

cation-anion pair in the asymmetric unit (Fig. 4.31). One N atom in the six-membered

piperazine ring (N2/C10/C11/N3/C13/C14) in the lomefloxacinium cation is

protonated which adopts a slightly distorted chair conformation with puckering

parameters Q, θ and φ of 0.565 (3) Å, 178.0 (3)° and 109 (58)° (Cremer & Pople,

1975). The dihedral angle between the mean planes of the piperazine ring

(N2/C10/C11/N3/C13/C14) and the 10-atom ring system of the quinolone group is

43.3 (5)°. The picrate anion interacts with the protonated N atom of an adjacent cation

through a bifurcated N—H···O three-center hydrogen bond. The dihedral angle

between the mean planes of the anion benzene and cation piperizine and quinoline

rings is 46.2 (9)° and 7.2 (2)°, respectively. The mean planes of the two o-NO2 and

single p-NO2 groups in the picrate anion are twisted by, 37.9 (5)°, 57.0 (8)° [using

predominant component (0.743 (4), O6A & O7A, of disordered O atoms] and 2.5 (1)°

with respect to the mean planes of the six-membered benzene ring. Bond distances

and angles (Allen et al., 1987) are in normal ranges. Strong N—H···O hydrogen

476

bonds in concert with weak π–π stacking interactions (Table 4.50) dominate the

crystal packing creating a 2-D network along [011] (Fig. 4.33). Classical hydrogen

bonds found for the present structure.


Dashed lines indicate N—H···O hydrogen bonds creating a 2-D

network along [011].

477

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