Supramolecular architectures ofN-acetyl-L-proline monohydrate andN-benzyl-L-proline

P. Rajalakshmi,a N. Srinivasan,a* R. V. Krishnakumar,a

Ibrahim Abdul Razakb and Mohd Mustaqim Roslib

aDepartment of Physics, Thiagarajar College, Madurai 625009, India, and bX-ray

Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM,

Penang, Malaysia

Correspondence e-mail: vasan692000@yahoo.co.in

Received 28 May 2013

Accepted 18 September 2013

The title compounds, N-acetyl-l-proline monohydrate,

C7H11NO3�H2O, (I), and N-benzyl-l-proline, C12H15NO2,

(II), crystallize in the monoclinic space group P21 with Z0 =

1 and Z0 = 2, respectively. The conformation of C� with respect

to the carboxylic acid group in (I) is C�-exo or UP pucker, with

the pyrrolidine ring twisted, while in (II), it is C�-endo or

DOWN, with the pyrrolidine ring assuming an envelope

conformation. The crystal packing interactions in (I) are

composed of two substructures, one characterized by an

R66(24) motif through O—H� � �O hydrogen bonds and the

other by an R44(23) ring through C—H� � �O interactions. In

(II), the crystal packing interactions consist of N—H� � �O and

C—H� � �O hydrogen bonds. Proline (Pro) exists in its neutral

form in (I) and is zwitterionic in (II). This difference in the

ionization states of Pro is manifested through the absence of

N—H� � �O and presence of O—H� � �O interactions in (I), and

the presence of N—H� � �O and absence of O—H� � �O

hydrogen bonds in (II). While C—H� � �O interactions are

present in both (I) and (II), the geometry of the synthons

formed by them and their mode of participation in inter-

molecular interactions is different. Though the title

compounds differ significantly in terms of modifications in

the Pro skeleton, the differences in their supramolecular

structures may also be viewed as a result of the molecular

recognition facilitated by the presence of a solvent water

molecule in (I) and the zwitterionic state of the amino acid in

(II).

Keywords: crystal structure; amino acids; proline compounds;zwitterions; supramolecular assemblies.

1. Introduction

Modified amino acids are known to enhance the chemical,

physical and biological properties of proteins (Anderson et al.,

2004). Due to their structural diversity and functional versa-

tility, they are widely used as chiral building blocks and mol-

ecular scaffolds in pharmaceutics (Taylor et al., 1998; Ryder et

al., 2000; Jeng et al., 2002). Proline (Pro) is a functional amino

acid that participates in the regulation of key metabolic

pathways essential for maintenance, growth, reproduction and

immunity (Wu, 2009). For instance, Pro-rich collagen is made

of a repeating sequence of amino acids, (Xaa–Yaa–Gly)n, in

which Pro is most commonly found in the Xaa and Yaa

positions. The effect of chemical modifications of Pro, viz.

3-Hyp [N-acetyl-3(S)-hydroxy-l-proline methyl ester mono-

hydrate (EHUNEA)] and 4-Hyp [N-acetyl-4(S)-hydroxy-l-

proline methyl ester monohydrate], on the conformational

stability of the collagen triple helix has already been estab-

lished (Jenkins et al., 2003; Berg & Prockop, 1973). The results

of a statistical analysis of Pro conformations using the Protein

Data Bank (PDB) (Berman et al., 2000) has revealed that the

presence of an amino acid that favours the C�-DOWN pucker

in the Xaa position and the C�-UP pucker in the Yaa position

typically stabilizes the collagen triple helix (Vitagliano et al.,

2001a); these classifications will be discussed in depth in x3.

The present paper describes the crystal structures of

N-acetyl-l-proline monohydrate, (I), and N-benzyl-l-proline,

(II). This study might prove useful since modifications of

amino acids with their N-terminus protected by an acetyl (Ac)

or benzyl (B) group are expected to lead to more stable and

potent analogues than unprotected ones (Yeon et al., 2006). In

this context, the present work investigates the role of O—

H� � �O, N—H� � �O and C—H� � �O hydrogen bonds in the

construction of supramolecular assemblies in the l-proline

analogues (I) and (II).

2. Experimental

2.1. Synthesis and crystallization

Samples of N-acetyl-l-proline and N-benzyl-l-proline were

purchased from Alfa Aesar. The compounds were dissolved

separately in water–ethanol mixtures and the solutions left

unperturbed for slow evaporation of the solvent. Rectangular

transparent colourless single crystals of both (I) and (II)

suitable for X-ray analysis were obtained from the respective

mother liquors after a couple of weeks.

organic compounds

1390 # 2013 International Union of Crystallography doi:10.1107/S010827011302581X Acta Cryst. (2013). C69, 1390–1396

Acta Crystallographica Section C

Crystal StructureCommunications

ISSN 0108-2701

2.2. Refinement

Crystal data, data collection and structure refinement

details are summarized in Table 1. In (I), all the H atoms,

except for the hydroxy and water H atoms, were placed in

geometrically calculated positions (methylene C—H = 0.99 A,

methine C—H = 1.00 A and methyl C—H = 0.98 A) and

refined using a riding model, with Uiso(H) = 1.5Ueq(C) for the

methyl group and 1.2Ueq(C) otherwise. The positions of the

hydroxy and water H atoms were refined freely, with refined

isotropic displacement parameters for the water H atoms and

Uiso(H) = 1.5Ueq(O) for the hydroxy group. The water O—H

bond lengths were restrained to be similar. In (II), all the H

atoms were placed in geometrically calculated positions

(N—H = 0.93 A, methylene C—H = 0.99 A, methine C—H =

1.00 A and aromatic C—H = 0.95 A) and refined using a riding

model, with Uiso(H) = 1.2Ueq(parent) for all H atoms. In both

compounds, because of the absence of significant anomalous

scattering effects, the Friedel pairs were merged [1423 in (I)

and 3243 in (II)]. The stereochemistry was assigned according

to the vendor’s description (see x2.1).

3. Results and discussion

Amino acids (I) (Fig. 1) and (II) (Fig. 2) both crystallize in the

monoclinic crystal system in the space group P21, with Z0 = 1 in

(I) and Z0 = 2 in (II). The amino acid molecule exists in its

neutral form in (I) but is zwitterionic in (II). There are two

independent molecules in the asymmetric unit of (II), labelled

(II-A) and (II-B). The pyrrolidine ring in (I) adopts a twisted

conformation, with atoms C3 and C4 deviating from the plane

defined by the rest of the ring atoms by �0.226 (2) and

0.384 (2) A, respectively, with the associated puckering para-

meters (Cremer & Pople, 1975) being Q = 0.3736 (11) A and

’ = 274.54 (15)�. In (II), the pyrrolidine rings of both mol-

ecules A and B adopt an envelope conformation, with atom C4

(C�) deviating from the plane defined by the rest of the ring

atoms by 0.625 (2) A in molecule A and 0.6178 (18) A in

molecule B. The associated puckering parameters are Q =

organic compounds

Acta Cryst. (2013). C69, 1390–1396 Rajalakshmi et al. � C7H11NO3�H2O and C12H15NO2 1391

Table 1Experimental details.

(I) (II)

Crystal dataChemical formula C7H11NO3�H2O C12H15NO2

Mr 175.18 205.25Crystal system, space group Monoclinic, P21 Monoclinic, P21

Temperature (K) 100 100a, b, c (A) 6.2876 (3), 10.7132 (5), 6.7764 (3) 8.7552 (7), 10.6254 (8), 11.2816 (8)� (�) 111.143 (1) 93.737 (2)V (A3) 425.73 (3) 1047.27 (14)Z 2 4Radiation type Mo K� Mo K�� (mm�1) 0.11 0.09Crystal size (mm) 0.33 � 0.29 � 0.20 0.49 � 0.35 � 0.24

Data collectionDiffractometer Bruker Kappa APEXII area-

detector diffractometerBruker Kappa APEXII area-

detector diffractometerAbsorption correction Multi-scan (SADABS; Sheldrick,

2008)Multi-scan (SADABS; Sheldrick,

2008)Tmin, Tmax 0.964, 0.978 0.958, 0.979No. of measured, independent and

observed [I > 2�(I)] reflections10935, 1605, 1577 18099, 4800, 4436

Rint 0.035 0.027

RefinementR[F 2 > 2�(F 2)], wR(F 2), S 0.025, 0.069, 1.09 0.033, 0.090, 1.10No. of reflections 1605 4800No. of parameters 119 271No. of restraints 2 1H-atom treatment H atoms treated by a mixture of

independent and constrainedrefinement

H-atom parameters constrained

��max, ��min (e A�3) 0.34, �0.34 0.35, �0.22

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figure 1The molecular structure of (I), showing the atom-labelling scheme.Displacement ellipsoids are drawn at the 50% probability level.

0.4111 (12) A and ’ = 102.26 (16)� for molecule A, and Q =

0.4060 (13) A and ’ = 106.01 (16)� for molecule B. The dihe-

dral angle between the plane of the carboxylic acid group and

that of the N-acetyl group in (I) is 74 (3)�, and the analogous

dihedral angles involving the benzyl group in (II) are 68.92 (3)

(molecule A) and 64.60 (3)� (molecule B). The benzyl ring in

(II) is gauche with respect to the C� atom, with torsion angles

of 64.04 (11) (molecule A) and 63.07 (10)� (molecule B). The

dihedral angles between the carboxylic acid group and the

mean plane of atoms N—C�—C�—C� are 72.54 (4)� in (I),

63.42 (5)� in (II-A) and 60.26 (5)� in (II-B).

The conformation of the pyrrolidine ring of Pro is broadly

classified into two types, with the N, C� (C2), C� (C3) and C�

(C5) atoms of the pyrrolidine ring remaining essentially planar

(Fig. 3), and the C� atom (C4) deviating above (UP) or below

(DOWN) this plane. In the UP (or C�-exo) conformation,

atom C� and the carbonyl group are on opposite sides of the

plane, whereas they are on the same side in the DOWN (or C�-

endo) conformation. The UP and DOWN conformations can

be identified by considering the distribution of the Pro side-

chain torsion angles and 1, 2, 3, 4 and 5. In particular,

UP is characterized by negative values of 1, 3 and 5 and

positive values of 2 and 4 (Nemethy et al., 1992). A search of

the Cambridge Structural Database (CSD, Version 5.32; Allen,

2002) for Pro geometry among small molecules returned 599

hits, by excluding duplicate structure determinations and by

considering structures that were metal free, not disordered,

not polymeric, without ions, having an R factor less than 0.075,

including either chemically modified or unmodified structures,

either cyclic or acyclic, and with and without peptide bonds. A

plot of 1 versus (Fig. 4) shows two dense clusters centred

around 1 = �25� for UP and 1 = 25� for DOWN. The

distribution of UP and DOWN shows that the two states are

organic compounds

1392 Rajalakshmi et al. � C7H11NO3�H2O and C12H15NO2 Acta Cryst. (2013). C69, 1390–1396

Figure 2The molecular structure of (II), showing the atom-labelling scheme.Displacement ellipsoids are drawn at the 50% probability level.

Figure 3The ring conformations of Pro. In the UP (or C�-exo) conformation, C�

and the carbonyl group are on opposite sides of the ring plane, whereasthey are on the same side in the DOWN (or C�-endo) conformation.

Figure 4Torsion angles 1 versus 1 of Pro analogues, denoted as triangles. In theelectronic version of the paper, blue filled triangles denote the titlecompounds.

Figure 5Overlays of the main skeletons of the title compounds and related prolineanalogues (Pro). For the sake of clarity, H and other atoms attached toPro atoms have been omitted. (a) A side view of the overlay of (I) andfive related N-Ac-Pro analogues (CSD refcodes; see x3). (b) A side viewof the overlay of (I) and (II).

equally populated, with 318 DOWN (53%) and 281 UP (47%)

out of a total of 599 prolines. This is in close agreement with

51% DOWN and 49% UP reported earlier (Vitagliano et al.,

2001b), based on 3424 proline residues retrieved from the

Protein Data Bank (Berman et al., 2000).

In order to compare the puckering of the pyrrolidine rings

in the title compounds with some closely related Pro ana-

logues, data available in the CSD were retrieved. A search for

l-proline with simple substitutions returned 34 hits (excluding

duplicate structure determinations, and considering only

structures that were metal free, not disordered, not polymeric,

without ions and having an R factor less than 0.075), out of

which the requirement for an N-terminus with Ac and

compounds closely related to (I) yielded five hits, viz. CSD

refcodes NPRPLN (Kamwaya et al., 1981), CEMBIF (Ajo et

al., 1984), EHUNEA (Jenkins et al., 2003), LEWXER

(Wookhyun et al., 2006) and SODJEB (Kotch et al., 2008). No

closely related analogues were available for (II). An overlay

diagram of (I) with the respective structurally related sets of

molecules through fitting of similar atoms about the C�—N

bond in the pyrrolidine ring skeleton is shown in Fig. 5(a).

Fig. 5(b) shows a similar overlay diagram of (I) and the two

molecules of (II).

From Fig. 5, it may be seen that the pyrrolidine ring adopts

an UP (or C�-exo) pucker conformation in (I) and SODJEB,

whereas the others, viz. EHUNEA, NPRPLN, LEWXER and

the two molecules in the asymmetric unit of (II), are in a

DOWN pucker. In CEMBIF, the five-membered pyrrolidine

ring is neither UP nor DOWN, i.e. it is planar, owing to the

double bond between the C� and C� atoms in the ring. It is also

observed that the C� atom, whose position relative to other

atoms of the pyrrolidine ring determines the UP or DOWN

puckering, participates in an intermolecular C—H� � �O inter-

action in (I), which is in the neutral state and UP puckered.

This interaction is absent in (II), which is in the zwitterionic

state and DOWN puckered. An analysis of Pro residues in the

CSD showed no relationship between ionization state and UP

or DOWN puckered modes.

The difference in the ionization state of Pro and its conse-

quence is apparent from the torsion angles 1 and 2. These

values are 154.81 (7) and�29.25 (12)�, respectively, in (I), and

agree well with those observed for Pro in the neutral state,

namely 163.73 and �17.41� in EHUNEA, 158.39 and �22.88�

in LEWXER, and 147.81 and �35.67� in SODJEB. Similarly,

organic compounds

Acta Cryst. (2013). C69, 1390–1396 Rajalakshmi et al. � C7H11NO3�H2O and C12H15NO2 1393

Table 3Selected geometric parameters (A, �) for (II).

O1A—C1A 1.2491 (12) O1B—C1B 1.2493 (14)O2A—C1A 1.2528 (13) O2B—C1B 1.2554 (13)C1A—C2A 1.5443 (15) C1B—C2B 1.5427 (14)

C5A—N1A—C2A—C3A �3.97 (11) C5B—N1B—C2B—C3B �1.15 (10)O1A—C1A—C2A—N1A 174.07 (9) O1B—C1B—C2B—N1B 175.86 (9)O2A—C1A—C2A—N1A �6.66 (13) O2B—C1B—C2B—N1B �3.78 (13)N1A—C2A—C3A—C4A 28.12 (10) N1B—C2B—C3B—C4B 25.53 (10)C2A—C3A—C4A—C5A �41.36 (11) C2B—C3B—C4B—C5B �40.42 (10)C3A—C4A—C5A—N1A 38.89 (12) C3B—C4B—C5B—N1B 39.58 (11)

Table 2Selected geometric parameters (A, �) for (I).

O1—C1 1.3230 (10) C1—C2 1.5151 (12)O2—C1 1.2175 (10)

O2—C1—C2—N1 �29.25 (12) C3—C4—C5—N1 �32.47 (9)O1—C1—C2—N1 154.81 (7) C4—C5—N1—C2 14.93 (9)N1—C2—C3—C4 �28.62 (9) C5—N1—C2—C3 8.66 (9)C2—C3—C4—C5 38.11 (9)

Figure 6Parts of the crystal structure of (I), showing (a) the formation of the R6

6(24) motif of a two-dimensional sheet of the supramolecular network throughthree O—H� � �O hydrogen bonds extending parallel to the (001) plane (purple in the electronic version of the paper), and (b) the formation of the R4

4(23)motif of a two-dimensional sheet through two C—H� � �O hydrogen bonds extending parallel to the (100) plane (blue). For the sake of clarity, H atomsbonded to C atoms have been omitted.

the values of 174.07 (9) and �6.66 (13)� for (II-A), and

175.86 (9) and�3.78 (13)� for (II-B), agree well with those for

zwitterionic Pro, viz. 170.56 and �6.86� in l-proline

(Kayushina & Vainshtein, 1965), 179.3 (4) and �1.87 (3)� in l-

proline monohydrate (Janczak & Luger, 1997), 178.5 (12) and

�1.34 (17)� in dl-proline (Myung et al., 2005), 175.42 (11) and

�5.44 (15)� in dl-proline monohydrate (Padmanabhan et al.,

1995), and 178.7 and�3.2� in hydroxy l-proline (Koetzle et al.,

1973). A comparison (Tables 2 and 3) of the side-chain torsion

angles () involving the N atom, unprotonated in (I) and

protonated in (II), reveals that the differences are not as

significant as those involving carboxylic acid and carboxylate

O atoms, the values. This is due to the fact that the carb-

oxylic acid/carboxylate groups are free to rotate about the

C�—C1 bond and that the N atom is sterically strained about

the C�—N bond, in addition to the strain due to substitution.

In terms of graph-set motifs (Bernstein et al., 1995), the

crystal packing interactions in (I) may be described as

composed of two substructures, one characterized through

O—H� � �O hydrogen bonds and the other through C—H� � �O

interactions (Table 4). In the first substructure, water atom

O1W as a donor links the molecules into a linear chain along

the a axis, in which carboxyl atom O2ii and acetyl atom O3i

participate as acceptors (see Table 4 for full details and

symmetry codes). These chains are interconnected through

the participation of atom O1W as an acceptor in an O1—

H1� � �O1W hydrogen bond, leading to an R66(24) motif which is

the characteristic unit of the two-dimensional supramolecular

sheets which lie parallel to the (001) plane (Fig. 6a). In the

second substructure, atoms C4 (C�) and methyl C7 act as

donors to carboxylic acid atoms O1iii (C4—H4A� � �O1iii) and

O2iv (C7—H7C� � �O2iv), forming a layer running parallel to

organic compounds

1394 Rajalakshmi et al. � C7H11NO3�H2O and C12H15NO2 Acta Cryst. (2013). C69, 1390–1396

Table 5Hydrogen-bond geometry (A, �) for (II).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

N1B—H1B� � �O1Bi 0.93 2.31 2.8945 (13) 120N1A—H1A� � �O2A 0.93 2.02 2.5973 (13) 119N1B—H1B� � �O2B 0.93 2.05 2.6259 (12) 118C2B—H2B� � �O1Aii 1.00 2.51 3.2649 (13) 132C6A—H6A� � �O2B 0.99 2.45 3.1520 (14) 127C6A—H6B� � �O1Aiii 0.99 2.29 3.2506 (14) 164C5B—H5D� � �O2Ai 0.99 2.29 3.0796 (14) 136C6B—H6C� � �O1Aii 0.99 2.36 3.2221 (14) 145C8B—H8B� � �O1Aii 0.95 2.54 3.3721 (14) 146C12B—H12B� � �O1Bi 0.95 2.43 3.2438 (15) 143

Symmetry codes: (i) �xþ 1; yþ 12;�zþ 1; (ii) x; y; zþ 1; (iii) �xþ 1; y þ 1

2;�z.

Table 4Hydrogen-bond geometry (A, �) for (I).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

O1W—H1W1� � �O3i 0.80 (2) 1.90 (2) 2.6923 (10) 175 (3)O1W—H2W1� � �O2ii 0.80 (2) 2.07 (2) 2.8507 (10) 166 (2)O1—H1� � �O1W 0.84 1.75 2.5684 (10) 163C4—H4A� � �O1iii 0.99 2.59 3.5501 (12) 163C7—H7C� � �O2iv 0.98 2.54 3.4406 (12) 152

Symmetry codes: (i) �x; y� 12;�z þ 1; (ii) �xþ 1; y� 1

2;�zþ 1; (iii) �xþ 1; y þ 12;�z;

(iv) �xþ 1; yþ 12;�z þ 1.

Figure 7Perspective views of the two-dimensional network in (I), showing (a) O—H� � �O hydrogen bonds (dashed lines) parallel to the a axis, revealing thetriangular wave-like chain assembly, and (b) C—H� � �O hydrogen bonds (dashed lines) parallel to the the c axis, revealing the sinusoidal wave-likeassembly.

the (100) plane through a characteristic R44(23) ring motif

(Fig. 6b and Table 4). These two substructures are interlaced

into the other at the monoclinic angle �, leading to a three-

dimensional network of O—H� � �O and C—H� � �O hydrogen

bonds. A perspective view of the first substructure parallel to

the b axis reveals a triangular wave-like chain (Fig. 7a), and

that of the second a sinusoidal wave-like assembly (Fig. 7b).

The fact that water participates in the intermolecular inter-

action pattern including all available O atoms (i.e. as donor to

carboxylic acid atom O2 and carbonyl atom O3, and as

acceptor to hydroxy atom O1), compared with the relatively

weak C—H� � �O interactions involving only the hydroxy and

carboxyl O atoms, illustrates that the overall crystal structure

of (I) is a result of molecular recognition facilitated by the

presence of the water molecule.

In (II), the crystal packing interactions consist of N—H� � �O

and C—H� � �O hydrogen bonds (Table 5). The absence of O—

H� � �O hydrogen bonds and the extensive occurrence of C—

H� � �O interactions in (II) are due to the zwitterionic state of

Pro. Molecules A and B in the asymmetric unit differ in their

conformations and also in the modes of participation of their

carboxylate groups in intermolecular interactions. In molecule

B, each carboxylate O atom participates in an N—H� � �O

hydrogen bond, one being intra- and the other intermolecular

in nature. In molecule A, carboxylate atom O2 participates in

intramolecular N—H� � �O hydrogen bonds similar to that

found in molecule B (N1A—H1A� � �O2A and N1B—

H1B� � �O2B), while the other carboxylate O atom participates

in extensive intermolecular C—H� � �O interactions. Thus, the

characteristic head-to-tail hydrogen bonding observed in the

crystal structures of amino acids (Suresh & Vijayan, 1983) is

seen in the aggregation of molecules B (Z2 sequence) but is

not observed for molecules A. This implies that the presence

of head-to-tail hydrogen bonds in substituted amino acids

bears no relationship to their ionization states. Both molecules

A and B separately form an S(5) ring through N1A—

H1A� � �O2A and N1B—H1B� � �O2B hydrogen bonds. Simi-

larly, they both form separate C(6) and C(8) chains parallel to

the b axis through C6A—H6B� � �O1Aiii and C12B—

H12B� � �O1Bi hydrogen-bonding interactions (Fig. 8; see

Table 5 for symmetry codes and full details). There are five

C—H� � �O intermolecular interactions between molecules A

and B. The interaction pattern involving these may be visua-

lized as made up of one R12(8) and two R1

2(7) ring motifs which

are formed through a combination of C6B—H6C� � �O1Aii,

C8B—H8B� � �O1Aii and C2B—H2B� � �O1Aii interactions.

Atom O1Aii acts as an acceptor in the formation of a four-

centred or trifurcated-acceptor (Steiner, 2003) hydrogen-

bonding interaction between molecules A and B. These motifs

are interconnected through two other C6A—H6A� � �O2B and

C5B—H5D� � �O2Ai interactions, leading to supramolecular

sheets (Fig. 9) which lie parallel to the bc plane.

4. Conclusions

It is seen that the differences in the nature of the substituents

added to the main proline scaffold, viz. acetyl in (I) and benzyl

in (II), has significantly altered their respective supra-

molecular architectures while their crystal symmetry is

retained. The presence of a water molecule in (I), and the

difference in the ionization states of (I) and (II), have effected

significant changes in their respective intermolecular schemes.

Yet no relationship could be established between the presence

or absence of water and the observed ionization state of Pro.

A survey of the CSD revealed that, out of a total of 97

organic compounds

Acta Cryst. (2013). C69, 1390–1396 Rajalakshmi et al. � C7H11NO3�H2O and C12H15NO2 1395

Figure 8Part of the crystal structure of (II), showing the formation of C(6) andC(8) chains extending parallel to the b axis through C6A—H6B� � �O1A*and C12B—H12B� � �O1B# hydrogen-bond interactions. Dashed linesindicate hydrogen bonds. For the sake of clarity, H atoms not involved inthe hydrogen bonding have been omitted. Atoms labelled with a hashsymbol (#) or an asterisk are at the symmetry positions (�x + 1, y + 1

2,�z)and (�x + 1, y + 1

2, �z + 1), respectively.Figure 9A packing diagram for (II), showing the formation of supramolecularsheets parallel to the bc plane and the separate R1

2(7) and R12(8) ring

motifs formed by molecules A and B (in the electronic version of thepaper, A molecules are shown in black and B molecules in red). Dashedlines indicate hydrogen bonds. H atoms not involved in the hydrogenbonding have been omitted.

structures containing Pro, water is present in only 31. Of these

31, Pro is in the neutral state in 15 and zwitterionic in 16. In the

remaining 66 structures with no water molecules, 37 were

found to be in the neutral state and 29 as zwitterions. These

statistics clearly reveal that the ionization state has no direct

relationship with the presence or absence of water molecules

in the crystal structure. However, it is important to note that,

while the neutral state of the amino acid molecule eliminates

the possibility of characteristic head-to-tail hydrogen bonds,

even in zwitterions where there is ample scope for head-to-tail

alignment, their occurrence is unpredictable. In addition, the

fact that both title compounds crystallize in the same space

group, in spite of their differences in the chemical and

geometric nature of the substituents, highlights the delicate

nature of the intermolecular forces and their relationship with

the conformation and ionization state of individual molecules,

and consequently the crystal symmetry.

The authors thank the Department of Biotechnology, New

Delhi, for their Star College Scheme under which the

Cambridge Structural Database was purchased and upgraded.

The authors thank Dr Mutharasu Devarajan, Associate

Professor, and the staff of the X-ray Crystallography Unit,

School of Physics, Universiti Sains Malaysia, for their help

with the data collection.

Supplementary data for this paper are available from the IUCr electronicarchives (Reference: MX3104). Services for accessing these data aredescribed at the back of the journal.

References

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organic compounds

1396 Rajalakshmi et al. � C7H11NO3�H2O and C12H15NO2 Acta Cryst. (2013). C69, 1390–1396

supplementary materials

sup-1Acta Cryst. (2013). C69, 1390-1396

supplementary materials

Acta Cryst. (2013). C69, 1390-1396 [doi:10.1107/S010827011302581X]

Supramolecular architectures of N-acetyl-L-proline monohydrate and N-benzyl-

L-proline

P. Rajalakshmi, N. Srinivasan, R. V. Krishnakumar, Ibrahim Abdul Razak and Mohd Mustaqim

Rosli

Computing details

For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction:

SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine

structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material

for publication: SHELXL97 (Sheldrick, 2008).

(prl021) N-Acetyl-L-proline monohydrate

Crystal data

C7H11NO3·H2OMr = 175.18Monoclinic, P21

Hall symbol: P 2yba = 6.2876 (3) Åb = 10.7132 (5) Åc = 6.7764 (3) Åβ = 111.143 (1)°V = 425.73 (3) Å3

Z = 2

F(000) = 188Dx = 1.367 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 3028 reflectionsθ = 3.2–32.6°µ = 0.11 mm−1

T = 100 KBlock, colourless0.33 × 0.29 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer

Radiation source: fine-focus sealed tubeGraphite monochromatorφ and ω scansAbsorption correction: multi-scan

(SADABS; Sheldrick, 2008)Tmin = 0.964, Tmax = 0.978

10935 measured reflections1605 independent reflections1577 reflections with I > 2σ(I)Rint = 0.035θmax = 32.6°, θmin = 3.2°h = −7→9k = −16→15l = −10→10

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.025wR(F2) = 0.069S = 1.091605 reflections119 parameters2 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

supplementary materials

sup-2Acta Cryst. (2013). C69, 1390-1396

w = 1/[σ2(Fo2) + (0.0487P)2 + 0.0228P]

where P = (Fo2 + 2Fc

2)/3(Δ/σ)max < 0.001

Δρmax = 0.34 e Å−3

Δρmin = −0.34 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 F2 > σ(F2) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

O1W 0.25777 (12) 0.10499 (7) 0.38337 (11) 0.01809 (14)O1 0.16647 (12) 0.30996 (6) 0.17278 (11) 0.01696 (13)H1 0.2142 0.2516 0.2606 0.025*O2 0.38606 (12) 0.42695 (7) 0.44520 (10) 0.01787 (14)O3 −0.05574 (12) 0.58499 (7) 0.32887 (12) 0.01871 (14)N1 0.20972 (13) 0.64355 (7) 0.19803 (12) 0.01394 (14)C1 0.25938 (14) 0.41643 (8) 0.26143 (13) 0.01349 (15)C2 0.20118 (14) 0.52137 (8) 0.10077 (13) 0.01355 (14)H2A 0.0470 0.5072 −0.0098 0.016*C3 0.38220 (17) 0.53084 (9) −0.00327 (15) 0.01792 (16)H3A 0.5336 0.5034 0.0952 0.022*H3B 0.3387 0.4800 −0.1339 0.022*C4 0.38250 (18) 0.67017 (10) −0.05307 (14) 0.02064 (18)H4A 0.5281 0.6951 −0.0668 0.025*H4B 0.2552 0.6914 −0.1856 0.025*C5 0.35274 (16) 0.73344 (9) 0.13729 (14) 0.01673 (16)H5A 0.5015 0.7458 0.2534 0.020*H5B 0.2752 0.8151 0.0978 0.020*C6 0.07107 (14) 0.66836 (8) 0.30458 (13) 0.01427 (15)C7 0.07690 (17) 0.79800 (9) 0.39021 (15) 0.01805 (16)H7A −0.0239 0.8026 0.4716 0.027*H7B 0.0253 0.8575 0.2726 0.027*H7C 0.2331 0.8186 0.4823 0.027*H1W1 0.198 (3) 0.095 (2) 0.467 (3) 0.034 (5)*H2W1 0.373 (3) 0.0642 (19) 0.427 (3) 0.027 (4)*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

O1W 0.0204 (3) 0.0162 (3) 0.0203 (3) 0.0031 (2) 0.0105 (2) 0.0035 (2)O1 0.0205 (3) 0.0125 (3) 0.0177 (3) −0.0015 (2) 0.0068 (2) −0.0003 (2)O2 0.0188 (3) 0.0167 (3) 0.0165 (3) −0.0013 (2) 0.0043 (2) 0.0018 (2)O3 0.0187 (3) 0.0184 (3) 0.0229 (3) −0.0033 (2) 0.0121 (2) −0.0015 (2)N1 0.0150 (3) 0.0125 (3) 0.0159 (3) −0.0013 (2) 0.0074 (2) 0.0007 (2)

supplementary materials

sup-3Acta Cryst. (2013). C69, 1390-1396

C1 0.0128 (3) 0.0129 (3) 0.0167 (3) 0.0001 (3) 0.0077 (3) 0.0007 (3)C2 0.0146 (3) 0.0132 (3) 0.0140 (3) −0.0008 (3) 0.0067 (3) 0.0000 (3)C3 0.0202 (4) 0.0191 (4) 0.0188 (4) −0.0007 (3) 0.0122 (3) 0.0003 (3)C4 0.0238 (4) 0.0228 (4) 0.0195 (3) −0.0023 (3) 0.0128 (3) 0.0037 (3)C5 0.0172 (3) 0.0156 (4) 0.0194 (3) −0.0024 (3) 0.0090 (3) 0.0028 (3)C6 0.0141 (3) 0.0148 (3) 0.0144 (3) 0.0008 (3) 0.0057 (2) 0.0008 (3)C7 0.0227 (4) 0.0138 (3) 0.0192 (3) 0.0003 (3) 0.0095 (3) −0.0003 (3)

Geometric parameters (Å, º)

O1W—H1W1 0.797 (17) C3—C4 1.5305 (15)O1W—H2W1 0.804 (17) C3—H3A 0.9900O1—C1 1.3230 (10) C3—H3B 0.9900O1—H1 0.8400 C4—C5 1.5272 (14)O2—C1 1.2175 (10) C4—H4A 0.9900O3—C6 1.2470 (11) C4—H4B 0.9900N1—C6 1.3439 (11) C5—H5A 0.9900N1—C2 1.4578 (11) C5—H5B 0.9900N1—C5 1.4739 (12) C6—C7 1.5006 (13)C1—C2 1.5151 (12) C7—H7A 0.9800C2—C3 1.5433 (13) C7—H7B 0.9800C2—H2A 1.0000 C7—H7C 0.9800

H1W1—O1W—H2W1 105 (2) C5—C4—H4A 111.0C1—O1—H1 109.5 C3—C4—H4A 111.0C6—N1—C2 119.68 (7) C5—C4—H4B 111.0C6—N1—C5 126.88 (8) C3—C4—H4B 111.0C2—N1—C5 112.78 (7) H4A—C4—H4B 109.0O2—C1—O1 124.26 (8) N1—C5—C4 102.64 (8)O2—C1—C2 124.45 (8) N1—C5—H5A 111.2O1—C1—C2 111.15 (7) C4—C5—H5A 111.2N1—C2—C1 112.42 (7) N1—C5—H5B 111.2N1—C2—C3 103.56 (7) C4—C5—H5B 111.2C1—C2—C3 110.50 (7) H5A—C5—H5B 109.2N1—C2—H2A 110.1 O3—C6—N1 119.93 (8)C1—C2—H2A 110.1 O3—C6—C7 122.64 (8)C3—C2—H2A 110.1 N1—C6—C7 117.43 (8)C4—C3—C2 102.98 (8) C6—C7—H7A 109.5C4—C3—H3A 111.2 C6—C7—H7B 109.5C2—C3—H3A 111.2 H7A—C7—H7B 109.5C4—C3—H3B 111.2 C6—C7—H7C 109.5C2—C3—H3B 111.2 H7A—C7—H7C 109.5H3A—C3—H3B 109.1 H7B—C7—H7C 109.5C5—C4—C3 103.67 (7)

C6—N1—C2—C1 −60.72 (10) C2—N1—C6—O3 3.61 (12)C5—N1—C2—C1 127.95 (8) C5—N1—C6—O3 173.60 (8)C6—N1—C2—C3 179.99 (7) C2—N1—C6—C7 −176.38 (7)C5—N1—C2—C3 8.66 (9) C5—N1—C6—C7 −6.39 (12)O2—C1—C2—N1 −29.25 (12) O1—C1—C2—N1 154.81 (7)

supplementary materials

sup-4Acta Cryst. (2013). C69, 1390-1396

O1—C1—C2—N1 154.81 (7) O2—C1—C2—N1 −29.25 (12)O2—C1—C2—C3 85.91 (10) N1—C2—C3—C4 −28.62 (9)O1—C1—C2—C3 −90.03 (9) C2—C3—C4—C5 38.11 (9)N1—C2—C3—C4 −28.62 (9) C3—C4—C5—N1 −32.47 (9)C1—C2—C3—C4 −149.23 (8) C4—C5—N1—C2 14.93 (9)C2—C3—C4—C5 38.11 (9) C5—N1—C2—C3 8.66 (9)C6—N1—C5—C4 −155.65 (8) C2—N1—C6—O3 3.61 (12)C2—N1—C5—C4 14.93 (9) C2—N1—C6—C7 −176.38 (7)C3—C4—C5—N1 −32.47 (9)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1W—H1W1···O3i 0.80 (2) 1.90 (2) 2.6923 (10) 175 (3)O1W—H2W1···O2ii 0.80 (2) 2.07 (2) 2.8507 (10) 166 (2)O1—H1···O1W 0.84 1.75 2.5684 (10) 163C4—H4A···O1iii 0.99 2.59 3.5501 (12) 163C7—H7C···O2iv 0.98 2.54 3.4406 (12) 152

Symmetry codes: (i) −x, y−1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y+1/2, −z; (iv) −x+1, y+1/2, −z+1.

(prl017) N-Benzyl-L-proline

Crystal data

C12H15NO2

Mr = 205.25Monoclinic, P21

Hall symbol: P 2yba = 8.7552 (7) Åb = 10.6254 (8) Åc = 11.2816 (8) Åβ = 93.737 (2)°V = 1047.27 (14) Å3

Z = 4

F(000) = 440Dx = 1.302 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 8043 reflectionsθ = 2.9–35.1°µ = 0.09 mm−1

T = 100 KBlock, colourless0.49 × 0.35 × 0.24 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer

Radiation source: fine-focus sealed tubeGraphite monochromatorφ and ω scansAbsorption correction: multi-scan

(SADABS; Sheldrick, 2008)Tmin = 0.958, Tmax = 0.979

18099 measured reflections4800 independent reflections4436 reflections with I > 2σ(I)Rint = 0.027θmax = 35.1°, θmin = 2.9°h = −14→14k = −15→17l = −18→18

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.033wR(F2) = 0.090S = 1.104800 reflections271 parameters1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

supplementary materials

sup-5Acta Cryst. (2013). C69, 1390-1396

w = 1/[σ2(Fo2) + (0.0561P)2 + 0.0405P]

where P = (Fo2 + 2Fc

2)/3(Δ/σ)max < 0.001

Δρmax = 0.35 e Å−3

Δρmin = −0.22 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 F2 > σ(F2) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

O1A 0.61856 (12) 0.32428 (9) −0.10200 (7) 0.02301 (18)O2A 0.59164 (11) 0.26347 (8) 0.08645 (7) 0.02138 (16)N1A 0.51397 (10) 0.48296 (9) 0.16407 (7) 0.01368 (14)H1A 0.5191 0.4008 0.1924 0.016*C1A 0.59243 (12) 0.34259 (10) 0.00415 (9) 0.01488 (16)C2A 0.55915 (11) 0.48054 (10) 0.03700 (8) 0.01252 (15)H2A 0.4748 0.5154 −0.0174 0.015*C3A 0.70109 (12) 0.56494 (10) 0.03644 (9) 0.01641 (17)H3A 0.7723 0.5347 −0.0220 0.020*H3B 0.6722 0.6531 0.0175 0.020*C4A 0.77286 (13) 0.55390 (12) 0.16281 (10) 0.0201 (2)H4A 0.8290 0.4736 0.1748 0.024*H4B 0.8432 0.6249 0.1826 0.024*C5A 0.63320 (14) 0.55859 (14) 0.23540 (10) 0.0238 (2)H5A 0.6556 0.5208 0.3148 0.029*H5B 0.5985 0.6464 0.2454 0.029*C6A 0.35512 (12) 0.53137 (10) 0.18130 (9) 0.01511 (17)H6A 0.3402 0.5367 0.2674 0.018*H6B 0.3447 0.6173 0.1478 0.018*C7A 0.23322 (12) 0.44849 (10) 0.12285 (9) 0.01500 (17)C8A 0.17069 (12) 0.47618 (12) 0.00899 (10) 0.01859 (18)H8A 0.2066 0.5470 −0.0325 0.022*C9A 0.05565 (13) 0.40030 (14) −0.04434 (11) 0.0229 (2)H9A 0.0145 0.4188 −0.1224 0.028*C10A 0.00116 (14) 0.29755 (13) 0.01659 (12) 0.0243 (2)H10A −0.0785 0.2468 −0.0191 0.029*C11A 0.06378 (14) 0.26948 (13) 0.12990 (12) 0.0234 (2)H11A 0.0274 0.1988 0.1712 0.028*C12A 0.17955 (13) 0.34423 (11) 0.18335 (10) 0.01825 (18)H12A 0.2219 0.3244 0.2608 0.022*O1B 0.36792 (11) 0.22077 (9) 0.50218 (8) 0.02390 (18)O2B 0.45376 (11) 0.40134 (9) 0.42551 (7) 0.02149 (16)N1B 0.52626 (10) 0.50874 (8) 0.63115 (7) 0.01357 (14)

supplementary materials

sup-6Acta Cryst. (2013). C69, 1390-1396

H1B 0.5289 0.5305 0.5515 0.016*C1B 0.42133 (12) 0.32975 (11) 0.50877 (9) 0.01606 (17)C2B 0.45124 (11) 0.38057 (9) 0.63626 (8) 0.01327 (16)H2B 0.5197 0.3214 0.6838 0.016*C3B 0.30385 (13) 0.40287 (11) 0.69983 (10) 0.01821 (18)H3D 0.2201 0.3478 0.6671 0.022*H3C 0.3206 0.3872 0.7862 0.022*C4B 0.26739 (14) 0.54111 (13) 0.67482 (11) 0.0231 (2)H4C 0.2194 0.5527 0.5937 0.028*H4D 0.1986 0.5755 0.7331 0.028*C5B 0.42344 (15) 0.60231 (11) 0.68773 (10) 0.0212 (2)H5C 0.4233 0.6842 0.6458 0.025*H5D 0.4563 0.6157 0.7724 0.025*C6B 0.68782 (12) 0.51302 (10) 0.68449 (8) 0.01598 (17)H6C 0.6897 0.4856 0.7684 0.019*H6D 0.7259 0.6007 0.6830 0.019*C7B 0.79154 (12) 0.42941 (10) 0.61778 (9) 0.01495 (17)C8B 0.83437 (13) 0.31084 (11) 0.66143 (10) 0.01866 (18)H8B 0.8003 0.2832 0.7353 0.022*C9B 0.92654 (14) 0.23287 (12) 0.59749 (11) 0.0223 (2)H9B 0.9549 0.1521 0.6275 0.027*C10B 0.97735 (14) 0.27332 (13) 0.48934 (11) 0.0220 (2)H10B 1.0402 0.2201 0.4455 0.026*C11B 0.93589 (13) 0.39185 (12) 0.44573 (10) 0.02041 (19)H11B 0.9711 0.4198 0.3723 0.024*C12B 0.84295 (12) 0.46949 (11) 0.50943 (9) 0.01682 (17)H12B 0.8143 0.5501 0.4791 0.020*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

O1A 0.0389 (5) 0.0188 (4) 0.0116 (3) 0.0033 (4) 0.0047 (3) −0.0028 (3)O2A 0.0343 (4) 0.0135 (3) 0.0168 (3) −0.0003 (3) 0.0050 (3) 0.0029 (3)N1A 0.0167 (3) 0.0148 (3) 0.0097 (3) −0.0013 (3) 0.0025 (2) −0.0004 (3)C1A 0.0195 (4) 0.0127 (4) 0.0125 (4) −0.0009 (3) 0.0018 (3) −0.0011 (3)C2A 0.0157 (4) 0.0129 (4) 0.0092 (3) −0.0003 (3) 0.0023 (3) 0.0004 (3)C3A 0.0178 (4) 0.0151 (4) 0.0166 (4) −0.0034 (3) 0.0034 (3) 0.0007 (3)C4A 0.0184 (4) 0.0236 (5) 0.0180 (4) −0.0044 (4) −0.0001 (3) −0.0037 (4)C5A 0.0222 (5) 0.0344 (6) 0.0151 (4) −0.0094 (5) 0.0025 (4) −0.0094 (4)C6A 0.0181 (4) 0.0139 (4) 0.0139 (4) 0.0006 (3) 0.0055 (3) −0.0013 (3)C7A 0.0151 (4) 0.0148 (4) 0.0157 (4) 0.0010 (3) 0.0047 (3) 0.0000 (3)C8A 0.0173 (4) 0.0212 (5) 0.0175 (4) 0.0019 (4) 0.0029 (3) 0.0016 (4)C9A 0.0181 (4) 0.0280 (5) 0.0225 (5) 0.0023 (4) 0.0000 (4) −0.0024 (4)C10A 0.0168 (4) 0.0248 (5) 0.0316 (6) −0.0017 (4) 0.0030 (4) −0.0058 (5)C11A 0.0202 (5) 0.0192 (5) 0.0318 (6) −0.0023 (4) 0.0073 (4) 0.0008 (4)C12A 0.0192 (4) 0.0161 (4) 0.0201 (4) −0.0001 (4) 0.0061 (3) 0.0019 (3)O1B 0.0297 (4) 0.0186 (4) 0.0243 (4) −0.0069 (3) 0.0089 (3) −0.0084 (3)O2B 0.0310 (4) 0.0214 (4) 0.0123 (3) −0.0027 (3) 0.0025 (3) −0.0004 (3)N1B 0.0192 (4) 0.0110 (3) 0.0109 (3) 0.0004 (3) 0.0040 (3) −0.0006 (3)C1B 0.0180 (4) 0.0164 (4) 0.0142 (4) −0.0001 (3) 0.0038 (3) −0.0035 (3)

supplementary materials

sup-7Acta Cryst. (2013). C69, 1390-1396

C2B 0.0159 (4) 0.0116 (4) 0.0125 (3) −0.0010 (3) 0.0030 (3) −0.0008 (3)C3B 0.0185 (4) 0.0199 (4) 0.0170 (4) −0.0006 (4) 0.0065 (3) −0.0012 (4)C4B 0.0237 (5) 0.0248 (5) 0.0216 (5) 0.0093 (4) 0.0078 (4) 0.0012 (4)C5B 0.0325 (6) 0.0127 (4) 0.0199 (4) 0.0040 (4) 0.0123 (4) −0.0012 (3)C6B 0.0208 (4) 0.0144 (4) 0.0126 (3) −0.0030 (3) −0.0001 (3) −0.0015 (3)C7B 0.0160 (4) 0.0141 (4) 0.0145 (4) −0.0022 (3) −0.0012 (3) 0.0003 (3)C8B 0.0188 (4) 0.0184 (5) 0.0186 (4) −0.0004 (4) −0.0001 (3) 0.0043 (4)C9B 0.0211 (5) 0.0200 (5) 0.0257 (5) 0.0036 (4) 0.0006 (4) 0.0048 (4)C10B 0.0194 (5) 0.0223 (5) 0.0244 (5) 0.0040 (4) 0.0022 (4) 0.0001 (4)C11B 0.0200 (4) 0.0226 (5) 0.0189 (4) 0.0013 (4) 0.0038 (3) 0.0017 (4)C12B 0.0182 (4) 0.0165 (4) 0.0158 (4) −0.0016 (4) 0.0010 (3) 0.0018 (3)

Geometric parameters (Å, º)

O1A—C1A 1.2491 (12) O1B—C1B 1.2493 (14)O2A—C1A 1.2528 (13) O2B—C1B 1.2554 (13)N1A—C6A 1.5072 (14) N1B—C6B 1.5013 (13)N1A—C5A 1.5077 (14) N1B—C5B 1.5104 (14)N1A—C2A 1.5120 (12) N1B—C2B 1.5146 (13)N1A—H1A 0.9300 N1B—H1B 0.9300C1A—C2A 1.5443 (15) C1B—C2B 1.5427 (14)C2A—C3A 1.5329 (14) C2B—C3B 1.5351 (15)C2A—H2A 1.0000 C2B—H2B 1.0000C3A—C4A 1.5246 (15) C3B—C4B 1.5255 (18)C3A—H3A 0.9900 C3B—H3D 0.9900C3A—H3B 0.9900 C3B—H3C 0.9900C4A—C5A 1.5162 (17) C4B—C5B 1.5116 (19)C4A—H4A 0.9900 C4B—H4C 0.9900C4A—H4B 0.9900 C4B—H4D 0.9900C5A—H5A 0.9900 C5B—H5C 0.9900C5A—H5B 0.9900 C5B—H5D 0.9900C6A—C7A 1.5026 (15) C6B—C7B 1.5065 (15)C6A—H6A 0.9900 C6B—H6C 0.9900C6A—H6B 0.9900 C6B—H6D 0.9900C7A—C8A 1.3945 (15) C7B—C8B 1.3950 (16)C7A—C12A 1.3985 (15) C7B—C12B 1.3963 (14)C8A—C9A 1.3955 (17) C8B—C9B 1.3906 (17)C8A—H8A 0.9500 C8B—H8B 0.9500C9A—C10A 1.391 (2) C9B—C10B 1.3935 (18)C9A—H9A 0.9500 C9B—H9B 0.9500C10A—C11A 1.3901 (19) C10B—C11B 1.3917 (18)C10A—H10A 0.9500 C10B—H10B 0.9500C11A—C12A 1.3935 (17) C11B—C12B 1.3912 (16)C11A—H11A 0.9500 C11B—H11B 0.9500C12A—H12A 0.9500 C12B—H12B 0.9500

C6A—N1A—C5A 111.21 (9) C6B—N1B—C5B 112.49 (8)C6A—N1A—C2A 115.38 (7) C6B—N1B—C2B 114.30 (8)C5A—N1A—C2A 107.48 (8) C5B—N1B—C2B 107.69 (8)C6A—N1A—H1A 107.5 C6B—N1B—H1B 107.3

supplementary materials

sup-8Acta Cryst. (2013). C69, 1390-1396

C5A—N1A—H1A 107.5 C5B—N1B—H1B 107.3C2A—N1A—H1A 107.5 C2B—N1B—H1B 107.3O1A—C1A—O2A 128.04 (10) O1B—C1B—O2B 128.25 (10)O1A—C1A—C2A 115.29 (9) O1B—C1B—C2B 114.84 (9)O2A—C1A—C2A 116.67 (9) O2B—C1B—C2B 116.91 (10)N1A—C2A—C3A 104.85 (8) N1B—C2B—C3B 105.00 (8)N1A—C2A—C1A 107.99 (8) N1B—C2B—C1B 109.08 (8)C3A—C2A—C1A 112.87 (8) C3B—C2B—C1B 113.13 (8)N1A—C2A—H2A 110.3 N1B—C2B—H2B 109.8C3A—C2A—H2A 110.3 C3B—C2B—H2B 109.8C1A—C2A—H2A 110.3 C1B—C2B—H2B 109.8C4A—C3A—C2A 103.64 (8) C4B—C3B—C2B 103.55 (9)C4A—C3A—H3A 111.0 C4B—C3B—H3D 111.1C2A—C3A—H3A 111.0 C2B—C3B—H3D 111.1C4A—C3A—H3B 111.0 C4B—C3B—H3C 111.1C2A—C3A—H3B 111.0 C2B—C3B—H3C 111.1H3A—C3A—H3B 109.0 H3D—C3B—H3C 109.0C5A—C4A—C3A 101.82 (9) C5B—C4B—C3B 102.68 (9)C5A—C4A—H4A 111.4 C5B—C4B—H4C 111.2C3A—C4A—H4A 111.4 C3B—C4B—H4C 111.2C5A—C4A—H4B 111.4 C5B—C4B—H4D 111.2C3A—C4A—H4B 111.4 C3B—C4B—H4D 111.2H4A—C4A—H4B 109.3 H4C—C4B—H4D 109.1N1A—C5A—C4A 104.41 (8) N1B—C5B—C4B 103.65 (9)N1A—C5A—H5A 110.9 N1B—C5B—H5C 111.0C4A—C5A—H5A 110.9 C4B—C5B—H5C 111.0N1A—C5A—H5B 110.9 N1B—C5B—H5D 111.0C4A—C5A—H5B 110.9 C4B—C5B—H5D 111.0H5A—C5A—H5B 108.9 H5C—C5B—H5D 109.0C7A—C6A—N1A 112.23 (8) N1B—C6B—C7B 111.39 (8)C7A—C6A—H6A 109.2 N1B—C6B—H6C 109.4N1A—C6A—H6A 109.2 C7B—C6B—H6C 109.4C7A—C6A—H6B 109.2 N1B—C6B—H6D 109.4N1A—C6A—H6B 109.2 C7B—C6B—H6D 109.4H6A—C6A—H6B 107.9 H6C—C6B—H6D 108.0C8A—C7A—C12A 119.51 (10) C8B—C7B—C12B 119.33 (10)C8A—C7A—C6A 120.37 (10) C8B—C7B—C6B 120.87 (10)C12A—C7A—C6A 120.11 (9) C12B—C7B—C6B 119.78 (10)C7A—C8A—C9A 120.28 (11) C9B—C8B—C7B 120.44 (10)C7A—C8A—H8A 119.9 C9B—C8B—H8B 119.8C9A—C8A—H8A 119.9 C7B—C8B—H8B 119.8C10A—C9A—C8A 120.10 (11) C8B—C9B—C10B 119.97 (11)C10A—C9A—H9A 119.9 C8B—C9B—H9B 120.0C8A—C9A—H9A 119.9 C10B—C9B—H9B 120.0C11A—C10A—C9A 119.70 (11) C11B—C10B—C9B 119.86 (11)C11A—C10A—H10A 120.2 C11B—C10B—H10B 120.1C9A—C10A—H10A 120.2 C9B—C10B—H10B 120.1C10A—C11A—C12A 120.52 (12) C12B—C11B—C10B 120.13 (11)C10A—C11A—H11A 119.7 C12B—C11B—H11B 119.9

supplementary materials

sup-9Acta Cryst. (2013). C69, 1390-1396

C12A—C11A—H11A 119.7 C10B—C11B—H11B 119.9C11A—C12A—C7A 119.89 (11) C11B—C12B—C7B 120.27 (10)C11A—C12A—H12A 120.1 C11B—C12B—H12B 119.9C7A—C12A—H12A 120.1 C7B—C12B—H12B 119.9

C6A—N1A—C2A—C3A 120.72 (9) C5B—N1B—C2B—C1B 120.39 (9)C5A—N1A—C2A—C3A −3.97 (11) O1B—C1B—C2B—N1B 175.86 (9)C6A—N1A—C2A—C1A −118.70 (9) O2B—C1B—C2B—N1B −3.78 (13)C5A—N1A—C2A—C1A 116.61 (10) O1B—C1B—C2B—C3B −67.67 (12)O1A—C1A—C2A—N1A 174.07 (9) O2B—C1B—C2B—C3B 112.68 (11)O2A—C1A—C2A—N1A −6.66 (13) N1B—C2B—C3B—C4B 25.53 (10)O1A—C1A—C2A—C3A −70.50 (12) C1B—C2B—C3B—C4B −93.32 (10)O2A—C1A—C2A—C3A 108.76 (11) C2B—C3B—C4B—C5B −40.42 (10)N1A—C2A—C3A—C4A 28.12 (10) C6B—N1B—C5B—C4B −150.76 (9)C1A—C2A—C3A—C4A −89.17 (10) C2B—N1B—C5B—C4B −23.91 (11)C2A—C3A—C4A—C5A −41.36 (11) C3B—C4B—C5B—N1B 39.58 (11)C6A—N1A—C5A—C4A −149.03 (10) C5B—N1B—C6B—C7B −173.70 (8)C2A—N1A—C5A—C4A −21.85 (12) C2B—N1B—C6B—C7B 63.07 (10)C3A—C4A—C5A—N1A 38.89 (12) N1B—C6B—C7B—C8B −100.93 (11)C5A—N1A—C6A—C7A −173.23 (9) N1B—C6B—C7B—C12B 77.58 (12)C2A—N1A—C6A—C7A 64.04 (11) C12B—C7B—C8B—C9B −0.40 (16)N1A—C6A—C7A—C8A −95.18 (11) C6B—C7B—C8B—C9B 178.12 (10)N1A—C6A—C7A—C12A 86.06 (11) C7B—C8B—C9B—C10B 0.33 (18)C12A—C7A—C8A—C9A −0.14 (16) C8B—C9B—C10B—C11B 0.12 (18)C6A—C7A—C8A—C9A −178.91 (10) C9B—C10B—C11B—C12B −0.50 (18)C7A—C8A—C9A—C10A 0.93 (18) C10B—C11B—C12B—C7B 0.43 (17)C8A—C9A—C10A—C11A −1.18 (19) C8B—C7B—C12B—C11B 0.02 (16)C9A—C10A—C11A—C12A 0.66 (19) C6B—C7B—C12B—C11B −178.52 (10)C10A—C11A—C12A—C7A 0.12 (18) C2A—N1A—C6A—C7A 64.04 (11)C8A—C7A—C12A—C11A −0.38 (16) C1A—C2A—N1A—C6A −118.70 (9)C6A—C7A—C12A—C11A 178.39 (10) C2B—N1B—C6B—C7B 63.07 (10)C6B—N1B—C2B—C3B 124.63 (8) C1B—C2B—N1B—C6B −113.83 (9)C5B—N1B—C2B—C3B −1.15 (10) C2A—N1A—C6A—C7A 64.04 (11)C6B—N1B—C2B—C1B −113.83 (9) C2B—N1B—C6B—C7B 63.07 (10)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1B—H1B···O1Bi 0.93 2.31 2.8945 (13) 120N1A—H1A···O2A 0.93 2.02 2.5973 (13) 119N1B—H1B···O2B 0.93 2.05 2.6259 (12) 118C2B—H2B···O1Aii 1.00 2.51 3.2649 (13) 132C6A—H6A···O2B 0.99 2.45 3.1520 (14) 127C6A—H6B···O1Aiii 0.99 2.29 3.2506 (14) 164C5B—H5D···O2Ai 0.99 2.29 3.0796 (14) 136C6B—H6C···O1Aii 0.99 2.36 3.2221 (14) 145C8B—H8B···O1Aii 0.95 2.54 3.3721 (14) 146C12B—H12B···O1Bi 0.95 2.43 3.2438 (15) 143

supplementary materials

sup-10Acta Cryst. (2013). C69, 1390-1396

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