research article synthesis, spectral, thermogravimetric

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 653540 11 pageshttpdxdoiorg1011552013653540

Research ArticleSynthesis Spectral Thermogravimetric XRDMolecular Modelling and Potential Antibacterial Studies ofDimeric Complexes with Bis Bidentate ONndashNO DonorAzo Dye Ligands

Bipin Bihari Mahapatra1 Ramani Ranjan Mishra1 and Ashish Kumar Sarangi2

1 PG Department of Chemistry GM Autonomous College Sambalpur Odisha 768 004 India2Department of Chemistry Government College of Engineering Kalahandi Bhawanipatna Odisha 766 002 India

Correspondence should be addressed to Bipin Bihari Mahapatra mahapatrabipinyahoocom

Received 14 May 2013 Accepted 23 September 2013

Academic Editor Mallikarjuna Nadagouda

Copyright copy 2013 Bipin Bihari Mahapatra et alThis is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

The dimeric complexes of Co(II) Ni(II) Cu(II) Zn(II) Cd(II) and Hg(II) with two new symmetrical ONndashNO donorbis bidentate (tetradentate) azo dye ligands LH

2= 441015840-bis(41015840-hydroxyquinolinolinylazo)diphenylsulphone and L1015840H

2= 441015840-

bis(acetoacetanilideazo)diphenylsulphone have been synthesized The metal complexes have been characterised by elementalanalytical conductance magnetic susceptibility IR electronic spectra ESR NMR thermogravimetry X-ray diffraction (powderpattern) spectra and molecular modelling studies The Co(II) and Ni(II) complexes are found to be octahedral Cu(II) complexesare distorted octahedral and a tetrahedral stereochemistry has been assigned to Zn(II) Cd(II) and Hg(II) complexes Thethermogravimetric study indicates that compounds are quite stable The energy optimized structures are proposed using thesemiempirical ZINDO1 quantum mechanical calculations The potential antibacterial study of the ligands and some metalcomplexes has been made with one gram positive bacteria Staphylococcus aureus and one gram negative bacteria E coli whichgives encouraging results Both the Co(II) complexes are found to possess monoclinic crystal system

1 Introduction

Azo dyes are found to be pharmacologically active and hencethey are used as chemotherapeutic agents in the manufactureof potential drugs [1 2] Azo dyes are also used as indicatorin the chemical laboratories and as preservative and dyeingagents in food industries [3] Besides their applicationsazo dyes can also form stable complexes with transitionaland nontransitional metal ions because of the presence ofazo (ndashN=Nndash) group [4ndash9] The present study reports thesynthesis of two new ONndashNO donor tetradentate azo dyesand their twelve dimeric complexes and characterization ofthese complexes are made by using various physicochemicalmethods Antibacterial study and thermogravimetric andmolecular modelling of the azo dyes and some metal com-plexes have also been described

2 Experimental

21 Materials The chemicals 441015840-diaminodiphenyl sul-phone 8-hydroxyquinoline and acetoacetanilide were EMerck grade The chlorides of Co(II) Ni(II) Cu(II) Zn(II)Cd(II) andHg(II) were of SRL grade All other reagents andsolvents were purchased from commercial sources and wereof analytical grade

22 Synthesis of the Azo Dye Ligands The azo dyes weresynthesized by the coupling reaction of the diazoniumchloride obtained from 441015840-diaminodiphenyl sulphone(001mol 20 g) with alkaline solution of 8-hydroxyquinoline(002mol 29 g) and acetoacetanilide (002mol 354 g)separately at 0ndash5∘C

2 Journal of Chemistry

Table 1 Analytical and physical data of the ligands and its complexes

Compounds Meltingpoint (∘C) Colour Metal found

(calculated) Nitrogen found

(calculated) Chlorine found

(calculated) 120583eff BM

LH2 110 Dark brown mdash 1456 (1500) mdashL1015840H2 85 Orange red 1300 (1341)[Co2LCl2(H2O)6] gt280 Brown 1326 (1378) 952 (983) 800 (831) 50[Co2L

1015840Cl2(H2O)6] gt280 Greenish yellow 1233 (1279) 86 (912) 725 (771) 51[Ni2LCl2(H2O)6] gt280 Brown 1319 (1374) 933 (983) 795 (831) 31[Ni2L

1015840Cl2(H2O)6] gt280 Brown 1230 (1275) 890 (913) 726 (771) 30[Cu2LCl2(H2O)6] gt280 Dark brown 1464 (1469) 966 (974) 791 (822) 18[Cu2L

1015840Cl2(H2O)6] gt280 Orange red 1361 (1365) 889 (903) 712 (763) 18[Zn2LCl2(H2O)2] gt280 Light brown 1600 (1643) 1017 (1055) 844 (892) mdash[Zn2L

1015840Cl2(H2O)2] gt280 Light brown 1483 (1517) 957 (975) 783 (823)[Cd2LCl2(H2O)2] gt280 Light brown 2495 (2426) 905 (944) 740 (798) mdash[Cd2L

1015840Cl2(H2O)2] gt280 Light brown 2301 (2352) 832 (879) 694 (743)[Hg2LCl2(H2O)2] gt280 Brown 3731 (3763) 723 (788) 607 (666) mdash[Hg2L

1015840Cl2(H2O)2] gt280 Buff 3501 (3543) 700 (742) 582 (627)LH2 = 441015840-bis(41015840-hydroxyquinolinolinylazo)diphenylsulphoneL1015840H2 = 441015840-bis(acetoacetanilideazo)diphenylsulphone

23 Synthesis of Metal Complexes The metal chlorides inethanol were mixed separately with ethanolic solution of theligands in 2 1 molar ratio and the resulting solutions wereheated to 60ndash70∘C for about one hour on a heating mantleThe solution was then cooled down to room temperature andthe pH was raised to sim7 by adding conc ammonia drop bydrop with stirring The solid complexes thus separated werethen washed with ethanol followed by ether and dried invacuum

24 Physical Measurements The elemental analysis (CH N)were carried out on elemental analyser Perkin-Elmer 2400while metals were determined by EDTA after decompos-ing the complexes with conc HNO

3 Conductance mea-

surements of the complexes were made using ToshniwalCL 01ndash06 Conductivity Bridge The magnetic susceptibilitywere made at RT by Gouy method using Hg[Co(CN)

4] as

calibrant IR spectra (KBr) were recorded using IFS 66Uspectrophotometer electronic spectra of the CoII NiII andCuII complexes in DMF were recorded on a Hilger-Wattuvispeck spectrophotometer ESR spectra of CuII complexwere recorded on a E

4-spectrometer and NMR spectra were

recorded on a Jeol GSX 400 with DMSO as solvent and TMSas internal standard X-ray diffraction (powder pattern) ofthe CoII complexes was recorded on a Phillips PW 113000diffractometer and the TG DTG and DTA of the complexeswere recorded on NETZSCH STA 409 CCD in nitrogenatmosphere at a heating rate of 10∘C per minute

25 Molecular Modelling Molecular modelling of the ligandand complexes has been made by Argus Lab 401

26 Antibacterial Activity The antibacterial activity of theazodye ligands and CoII NiII CuII and ZnII complexes were

studied as per cup-plate method [10] using two strains ofbacteria like Staphylococcus aureus and E coli The solutionsof the test compounds are prepared in dimethylsulfoxide(DMSO) at 500 120583gmL The bacterial strains are inoculatedinto 100mL of the sterile nutrient broth and incubated at37 plusmn 1

∘C for 24 hoursThe density of the bacterial suspensionis standardized by McFarland method A well of uniformdiameter (6mm) is made on agar plates after inoculatingthem separately with the test organisms aseptically Thestandard drug and the test compounds are introduced withthe help of micropipette and the plates are placed in therefrigerator at 8ndash10∘C for proper diffusion of drug into themedia After two hours of cold incubation the petri platesare transferred to incubator and maintained at 37 plusmn 2

∘C for18ndash24 hours Then the petri plates are observed for zone ofinhibition by using vernier scale The results are reportedby comparing the zone of inhibition shown by the testcompounds with standard drug tetracycline The results arethe mean value of zone of inhibition of three sets measuredin millimetre

3 Results and Discussion

The physical characteristics and microanalytical data ofthe ligands and the complexes are given in (Table 1) Theanalytical data of the complexes revealed 2 1 molar ratio(metal ligand) which corresponds well with the generalformula [M

2LL1015840Cl

2(H2O)6] and [M1015840

2LL1015840Cl

2(H2O)2] where

M = CoII NiII CuII M1015840 = ZnII CdII HgII LH2= 441015840-bis

(41015840-hydroxyquinolinylazo)diphenylsulphone C30H20N6O4S

(Calcd () C 6428 H 36 N 1499 Found () C 638H 33 N 145) L1015840H

2= 441015840-bis(acetoacetalidoazo)diphen-

ylsulphone C32H30N6O6S (Calculated () C 6133 H 483

N 1341 Found () C 611 H 46 N 132) All the complexes

Journal of Chemistry 3

Table 2 Infrared spectra of the ligand and the complexes in cmminus1

Compounds ](CndashO) (phenolic)](CndashO) (enolic) ](CndashN)](C=O) ](MndashO) ](MndashN)LH2 1148 1407 mdash mdashL1015840H2 1263 1668 mdash mdash[Co2LCl2(H2O)6] 1133 1324 508 450[Co2L

1015840Cl2(H2O)6] 1240 1648 514 460[Ni2LCl2(H2O)6] 1135 1325 510 452[Ni2L

1015840Cl2(H2O)6] 1243 1645 513 455[Cu2LCl2(H2O)6] 1135 1330 510 450[Cu2L

1015840Cl2(H2O)6] 1233 1643 512 458[Zn2LCl2(H2O)2] 1134 1325 508 452[Zn2L

1015840Cl2(H2O)2] 1235 1645 511 457[Cd2LCl2(H2O)2] 1133 1324 510 450[Cd2L

1015840Cl2(H2O)2] 1240 1640 514 455[Hg2LCl2(H2O)2] 1135 1330 508 452[Hg2L

1015840Cl2(H2O)2] 1245 1642 510 460

are amorphous in nature and have high melting points andare insoluble in common organic solvents like methanolethanol and benzene but soluble in dimethylformamideand dimethylsulfoxide Nonelectrolytic nature of the com-plexes is indicated from the low conductance values (42ndash56Ωminus1 cm2molminus1) in 10minus3M solution in DMF [11]

31 IR Spectra In the IR spectra of the azodye ligands(Table 2) a broad band obtained at 3390 cmminus1 (LH

2) and at

3443 cmminus1 (L1015840H2) be assigned to OndashHsdot sdot sdotN and OndashHsdot sdot sdotO

intramolecular hydrogen bonding The absence of this bandin the spectra ofmetal complexes indicates the deprotonationof hydrogen bondedNsdot sdot sdotHorOsdot sdot sdotHgroup on complexationand subsequent coordination of the phenolicenolic oxygenatoms to the metal ions [12] The sharp band of the ligandsappear at 1625 cmminus1 (LH

2) and at 1633 cmminus1 (L1015840H

2) can be

attributed to ](ndashN=Nndash) vibration There is no shift of thisband in the metal complexes indicating noncoordinationof the azo group to the metal ions The band observedat 1148 cmminus1 (LH

2) is attributed to ](CndashO) vibration and

the bathochromic shift of sim15 cmminus1 in the metal complexesindicates bonding of oxine oxygen to the metal ions [13] Inthe spectrum of the ligand (LH

2) an intense band is observed

at 1407 cmminus1 due to CndashN vibration of the oxinate group[14] In the metal complexes this band occurs at sim1324 cmminus1The shift of this band to lower frequency regions showsconsiderably lower double bond character of the CndashN bonddue to involvement of the ring nitrogen on complexation[15 16] In the ligand (L1015840H

2) the band observed at 1668 cmminus1

can be assigned to ](C=O) vibration and shifting of thisband by 20ndash25 cmminus1 to lower frequency region in the metalchelates indicates the coordination of the amidic oxygenatoms to the metal ions The band shown at 1263 cmminus1 in theligand (L1015840H

2) can be assigned to enolic (CndashO) vibration and

decrease of this frequency by 20ndash30 cmminus1 on complexationis indicative of bonding of enolic oxygen atoms to the metalions In the metal complexes broad bands appear at sim3350ndash3399 cmminus1 followed by sharp peaks at sim833ndash842 cmminus1 and at

sim727ndash736 cmminus1 assignable to ndashOH starching rocking andwagging vibrations respectively indicating the presence ofcoordinated water molecules in the complexes [17] Theconclusive evidence of bonding of the azo dye ligands to themetal ions is proved by the appearance of bands at sim508ndash514 cmminus1 ](MndashO) and sim450ndash460 cmminus1 ](MndashN) [18]

32 Electronic Spectra and Magnetic Measurements In theelectronic spectrum of CoII complexes four ligandfield bands are observed at 8200(8250) 16400( 16500)19730(19960) and 31545(32450) cmminus1 The first threebands can be attributed to 4T

1g (F) rarr4T2g (F) (]

1)

rarr4A2g (F) (]2) and rarr

4T1g (P) (]

3) transitions respec-

tively and the fourth band is assigned to a CT bandThe ligand field parameters like Dq = 820(825) cmminus1B = 7686(7806) cmminus1 120573

35= 0790(0804) cmminus1 ]

2]1

= 2(2) and 120590 = 2658(2437) suggest an octahedralstereochemistry for the CoII complexes [19] In the electronicspectra of NiII complexes four ligand field bands areobserved at 10115(10140) 16930(17125) 24825(24975) and31345(32165) cmminus1 assignable to 3A

2g (F) rarr3T2g (F) (]1)

rarr3T1g (F) (]2) rarr

3T1g (P) (]3) andCT transition respec-

tively in an octahedral geometryThe ligand field parameterslike Dq = 10115(1014) cmminus1 B = 760(77933) cmminus112057335

= 0730(0748) cmminus1 ]2]1= 1673(1688) and 120590 =

3698(3368) also confirm an octahedral symmetry forthe complexes [20] The electronic spectra of the copper(II)complexes exhibit one broad band at 13300ndash14470 cmminus1 withmaxima at 13320(13345) cmminus1 assignable to 2Eg rarr

2T2g

transition in support of a distorted-octahedral configurationof the copper (II) complex [21 22] The magnetic momentof the metal complexes were recorded at RT The observedmagneticmoment value of the CoII NiII and CuII complexesare found to be sim50 sim31 and sim18 BM respectivelyindicating octahedral configuration of the complexes whichis further supported by their electronic spectral data [23 24]


Figure 1 Optimised geometry of ligand (LH2)

Figure 2 Optimised geometry of ligand (L1015840H2)

33 1H-NMR Studies The 1H NMR spectra of the ligandsLH2and L1015840H

2were recorded in DMSOThe complex pattern

observed at 120575 6746ndash9344 ppm and at 120575 7039ndash7956 ppmcorresponds to eighteen phenyl protons in each ligandThe sharp peak obtained at 120575 13629 ppm LH

2corresponds

to two phenolic protons The sharp peaks obtained at 120575

3570 ppm at 120575 2507 ppm 120575 10913 ppm and at 120575 13026 ppmin the ligand L1015840H

2correspond to six methyl (ndashCH

3) pro-

tons two methylene (gtCH) protons two amino (gtNH)protons and two enolic (gtCndashOH) protons respectively [25](Figures 5(a) and 5(b))

34 ESR Studies The ESR spectra of the CuII Complexes[Cu2LCl2(H2O)6] and [Cu

2L1015840Cl2(H2O)6] have been recorded

at X-band at RT The ldquogavrdquo values of the complexes arefound to be 209623 and 208807 respectively by applyingKneubuhlrsquos method [26] This type of spectrum may be dueto dynamic or pseudorotational type of Jahn-Teller distortion(Figures 6(a) and 6(b)) The spin-orbit coupling constant (120582)can be calculated from the equation

gav = 2(1 minus 2120582

10Dq) (1)

The 120582 value of the former complex is found to beminus320445 cmminus1 and that of latter complex is minus293823 cmminus1The decrease of the 120582 values of the complexes from the freeion value (minus830 cmminus1) indicates the overlapping of metal-ligand orbitals in the metal complexes

35 Powder XRD Studies The XRD study (powder pattern)of the complexes [Co

2LCl2(H2O)6] and [Co

2L1015840Cl2(H2O)6]

has been made with the help of X-ray diffractometer withCu as anode material K-alpha [nm] = 0154060 and thegenerator settings 30mA 40KV The prominent peaks of

Figure 3 Optimised geometry of [Co2LCl2(H2O)6] complex

Figure 4 Optimised geometry of [Co2L1015840Cl2(H2O)6] complex

X-ray diffraction pattern have been indexed and analysedby using computer programme from LSUCRPC [27] Thelattices parameters like 119886 119887 119888 120572 120573 120574 and 119881 (volume) areshown in (Tables 4(a) and 4(b)) along withmiller indices ℎ119896119897The indexing is confirmed by comparing between observedand calculated (2120579) values It is observed that the peaks ofthe XRD powder pattern (Figures 7(a) and 7(b)) that havesuccessfully indexed as figure of merit (119872) is found to be69 and 88 respectively as suggested by de Woulff [28] Thedensity (119889) of the complex was determined by the floatationmethod in a saturated solution of KBr NaCl and benzeneseparately The number of formula units per unit cell (119899) iscalculated from the relation

119899 =119889119873119881

119872 (2)

where 119889 = density of the compound119873 = Avogadrorsquos number119881 = volume of the unit cell and 119872 = molecular weightof the complex The value of ldquo119899rdquo is found to be 2 in bothcases which agrees well with the suggested structure of thecomplexes The crystal system of both the complexes wasfound to be monoclinic The Debye-Scherrer equation in X-ray diffraction and crystallography is a formula which relatesthe size of the crystallites in a solid to the broadening of a peakin a diffraction pattern The Debye-Scherrer equation is

119861 =119896120582

119904 sdot cos 120579 (3)

where 119904 = crystallite size 120582 = wavelength of X-ray radiation(CuK120572 = 0154060 nm) 119896 = constant taken as 094 120579 =diffraction angle (2308)∘ and119861= full width at halfmaximumheight (FWHM) (252 nm)The crystallite size of the complex[CO2LCl2(H2O)6] is found to be 499 nm For the other

complex [CO2L1015840Cl2(H2O)6] 120579 = diffraction angle (1829)∘


Current data parameters

Name May 29-201241

EXPNOPROCNO

F2-acquisition parametersDate 20120529Time 1340INSTRUM SpectPROBHD 5 mm PABBO BB-PULPROG zg30TD 32768Solvent DMSONS 32DS 2SWHFiders 0315264 HzAQRGDWDETE 2963 KD1TD0

10330578 Hz

15860212 s203

100000000 s1

Channel f1

NUC1 1 HP1PL1 000 dBPL1W 2353637505 WSFO1 5001330885 MHzF2-processing parametersSI 32768SF 5001300000 MHzWDWSSB 0LB 030 HzGB 0PC 100

EM

01234567891011121314(ppm)

100 3

209

910

340

1354

10

276

59

90

007

A22middot middot middotMishra

650 120583s48400 120583s

1065 120583s

(a)

01234567891011121314

100

098

034

230

036

036

420

077

244

117

111

070

057

088

(ppm)

B22 middot middot middotMishra


Name May 29-201231

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

650 120583s48400 120583s

1065 120583s

(b)

Figure 5 (a) 1H NMR spectra of LH2 (b) 1H NMR spectra of L1015840H

2


(a)

(b)

Figure 6 (a) ESR spectra of the [Cu2LCl2(H2O)6] complex (b) ESR spectra of the [Cu

2L1015840Cl2(H2O)6] complex

0 20 40 60 80 1002120579

0

2

4

6

8

Inte

nsity

(am

u)

Powder XRD

(a)

0 20 40 60 80 1002120579

0

10

20

30

40

50

60

Inte

nsity

(b)

Figure 7 (a) XRD graph for [Co2LCl2(H2O)6] complex (b) XRD graph for [Co



(a) (b)

(c)

Figure 8 (a) TGDTA graph of [Ni2L1015840Cl2(H2O)6] complex (b) TGDTA graph of [Co

2L1015840Cl2(H2O)6] complex (c) TGDTA graph of

[Ni2LCl2(H2O)6] complex

and 119861 = full width at half maximum height (FWHM)(277 nm) So crystallite size of this complex is found to be261 nm [29]

36 Thermogravimetric Study The complex [Ni2L1015840Cl2

(H2O)6] suffers a mass loss of 34 at 100∘C which corre-

sponds to the removal of two lattice held H2O molecules

supported by an endothermic peak on the DTA curve at 95∘C[30] Again the complex moiety loses a mass of 2352 at250∘C indicating removal of all coordinated H

2O molecules

and 16th of the ligand mass supported by an endothermicpeak at about 240∘C on the DTA curve Thereafter at 450∘Ccompound loses a mass of 2307 which corresponds tothe removal of 13rd of the ligand moiety supported by anexothermic peak at 420∘C Again the compound loses a massof 375 indicating removal of 23rd of the ligand moietyAgain the compound loses 55 mass which corresponds tothe removal of rest of the ligand moiety and two chlorineatoms and formation of NiO as residue (Figure 8(a))The complex [Co

2L1015840Cl2(H2O)6] loses a mass of 116 at

150∘C with the removal of all coordinated H2O molecules

supported by an endothermic peak at 140∘C on the DTAcurve Then the compound loses a mass of 135 indicatingremoval of 16th of the ligand moiety supported by anendothermic peak at 240∘C Thereafter the complex moietysuffers a mass loss of 1515 at 400∘C which corresponds tothe removal of 15th of the ligand moiety supported by anendothermic peak at 380∘C Finally the compound loses amass of 64 at 700∘C indicating removal of rest of the ligandmoiety and two chlorine atoms with the formation of CoOas the residue (Figure 8(b)) The complex [Ni

2LCl2(H2O)6]

suffers a mass loss of 2352 at 150∘C indicating removalof all the coordinated H

2O molecules along with 16th of

the ligand supported by an endothermic peak at 140∘C onthe DTA curve Then the compound loses a mass of 2424at 400∘C which corresponds to the removal of 13rd of theligand moiety supported by an exothermic peak at 325∘C onthe DTA curve Finally the compound loses 64 of massindicating removal of rest of the ligand moiety and twochlorine atoms which is supported by an endothermic peak


Table 3 (a) Selected bond lengths and bond energies of theligand (LH2) (b) Selected bond angles and bond energies of theligand (LH2) (c) Selected bond lengths and bond energies of theligand (L1015840H2) (d) Selected bond angles and bond energies of theligand (L1015840H2) (e) Selected bond lengths and bond energies ofthe [Co2LCl2(H2O)6] complex (f) Selected bond angles and bondenergies of the [Co2LCl2(H2O)6] complex (g) Selected bond lengthsand bond energies of the [Co2L

1015840Cl2(H2O)6] complex (h) Selectedbond angles and bond energies of the [Co2L

1015840Cl2(H2O)6] complex

(a)

Bond length in (A) Bond energy in KcalmoleC1ndashC4 (1379) 462660C5ndashS7 (1800) 294226S7ndashO8 (1568) 534855C2ndashN10 (1434) 546821C21ndashN26 (1343) 462660N10ndashN11 (1270) 1047330O31ndashC37 (1407) 523501

(b)

Bond angle in (A) Bond energy in KcalmoleC5ndashC6ndashC3 (12000) 222595C4ndashC5ndashS7 (12000) 200910C1ndashC2ndashN10 (12000) 278835C5ndashS7ndashC19 (9210) 206592C19ndashS7ndashO8 (9210) 298680C14ndashN12ndashN13 (10670) 425168O8ndashS7ndashO9 (9210) 451759C21ndashC20ndashO30 (12000) 259618C20ndashO30ndashH33 (10451) 164040

(c)

Bond length in (A) Bond energy in KcalmoleC1ndashC2 (1379) 462660C5ndashS7 (1800) 294226S7ndashO8 (1568) 534855C2ndashN10 (1434) 546821N10ndashN11 (1270) 1047330O24ndashC21 (1305) 656288

(d)

Bond angle in (A) Bond energy in KcalmoleC1ndashC2ndashC3 (12000) 222595C6ndashC5ndashS7 (12000) 200910C1ndashC2ndashN10 (12000) 278835C5ndashS7ndashC19 (9210) 206592C19ndashS7ndashO8 (9210) 298680C2ndashN10ndashN11 (10670) 425168

(e)

Bond length in (A) Bond energy in KcalmoleCo42ndashO45 (1964) 244913Co42ndashCl43 (2359) 144176

(e) Continued

Bond length in (A) Bond energy in KcalmoleCo42ndashN26 (1957) 273796

(f)

Bond angle in (A) Bond energy in KcalmoleO30ndashCo42ndashN26 (9000) 273401O30ndashCo42ndashO45 (9000) 245869N26ndashCo42ndashCl43 (9000) 202927Cl43ndashCo42ndashO45 (9000) 182786C27ndashN26ndashCo42 (12000) 157894N41ndashCo47ndashO50 (9000) 273401

(g)

Bond length in (A) Bond energy in KcalmoleCo54ndashO55 (2359) 144172Co54ndashO58 (1966) 244000

(h)

Bond angle in (A) Bond energy in KcalmoleC21ndashO24ndashCo54 (104470) 315920O24ndashCo54ndashO25 (9000) 245869O25ndashCo54ndashCl55 (9000) 182786Co59ndashO63ndashH75 (10451) 96017

Table 4 (a) X-ray diffraction data of the complex [Co2LCl2(H2O)6](b) X-ray diffraction data of the complex [Co2L

1015840Cl2(H2O)6]

(a)

Observed 2120579 Calculated 2120579 119889 spacing ℎ 119896 119871 Difference 21205791057 1058 8357 0 1 1 0011169 1170 7560 0 0 2 0011281 1278 6920 1 0 2 003119886 = 22571 A 120572 = 90∘ volume (119881) = 342329 A3 figure of merit = 68119887 = 10031 A 120573 = 96785∘ density (119889) = 0880 g cmminus3 Bravais lattice = 119901119888 = 15226 A 120574 = 900∘ number of unit cell (119899) = 2Probable crystal system = monoclinic

(b)

Observed 2120579 Calculated 2120579 119889 spacing ℎ 119896 119871 Difference 21205791009 1008 8770 1 0 0 0011341 1346 6575 0 1 0 0051557 1562 5667 0 3 0 0051749 1748 5069 1 1 1 001119886 = 15682 A 120572 = 90∘ volume (119881) = 109049 A3 figure of merit = 88119887 = 10596 A 120573 = 98070∘ density (119889) = 277 g cmminus3 Bravais lattice = 119901119888 = 6628 A 120574 = 90∘ number of unit Cell (119899) = 2Probable crystal system = monoclinic

Table 5 Kinetic parameters of the complexes

Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087


Table 6 Antibacterial activities of the ligands and the complexes (data presented as diameter of zone of inhibition mm)

Serial no Compound Concentration E coli (MTCC-40) Staphylococcus aureus (MTCC-87)1 LH2 500 120583gmL 12 142 L1015840H2 500 120583gmL 15 173 [Co2LCl2(H2O)6] 500 120583gmL 18 224 [Co2L

1015840Cl2(H2O)6] 500 120583gmL 17 205 [Ni2LCl2(H2O)6] 500 120583gmL 27 216 [Ni2L

1015840Cl2(H2O)6] 500 120583gmL 25 197 [Cu2LCl2(H2O)6] 500 120583gmL 28 238 [Cu2L

1015840Cl2(H2O)6] 500 120583gmL 26 209 [Zn2LCl2(H2O)2] 500 120583gmL 18 1510 [Zn2L

1015840Cl2(H2O)2] 500 120583gmL 16 1211 Tetracycline 1mgmL 45 30

at 930∘C on the DTA curve with the formation of NiO as theresidue (Figure 8(c))

The kinetic parameters such as order of reactionand activation energy for the thermal decomposition of[Cu2L1015840Cl2(H2O)6] [Ni2LCl2(H2O)6] and [Ni

2L1015840Cl2(H2O)6]

complexes have been determined by Freeman-caroll [31]method In this method the equation used is

minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)

where 119877119867= rate of heating 119908 = weight fraction of reacting

materials 119864119886= activation energy 119899 = order of reaction and

119911 = frequency This equation in the difference form will beΔ log119877119879 = 119899Δ log119908 minus (1198641198862303119877) sdot Δ1119879 when Δ(1119879)

is kept constant a plot at Δlog119877119879 versus Δlog119882 will givea linear relationship whose slope and intercept provide thevalue of 119899 and119864 respectivelyThe order of the decompositionreaction the activation energy and correlation coefficientare given in (Table 5) The calculated values of the activationenergy is found to be low due to the autocatalytic [32 33]effect of the metal ion on the thermal decomposition of thecomplex

37 Optimized Geometry Studies of the Ligands amp Complexesby Molecular Modelling Method Molecular modelling of theligands (LH

2) (L1015840H

2) and metal complexes of Co(II) have

been carried out using molecular mechanics and Hartree-Fock (HF) Quantum methods The standard 6ndash31 g basic setwas used in conjugationwith theHFmethod All calculationsare made using Gaussian 98 programme package [34ndash37]

The metal complexes were built and the optimization oftheir geometries was done at mmHndashF6ndash31 g level of theoryFigures 1 2 3 and 4 The findings of these computed worksare in good agreement with the experimental results Theselected bond lengths bond angles of the ligand bond anglesof the complexes and their bond energies are given in Tables3(a) 3(b) 3(c) 3(d) 3(e) 3(f) 3(g) and 3(h) respectivelyThetotal energies of both the complexes have been found to be287403 kcalmole and 247322 kcalmole respectively

0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11

E coliStaphylococcus aureus

Figure 9 Effect of the complexes on the growth of selected E coliand S aureus

38 Antibacterial Activity The ligands and metal complexeshave been screened for antibacterial activities and results havebeen shown in (Table 6) The antibacterial activity of thecompounds is examined against two strains of bacteria onegram positive Staphylococcus aureus and one gram negativeE coli The effectiveness of the compounds is classified intothree categories Sensitive intermediate and resistant If acompound is sensitive to a bacteria then it can be applied tocure the disease caused by the bacteria while it fails to do soif it is resistant to the bacteria Accordingly the effectivenessof the compound can be predicted by knowing the zoneof inhibition value in mm The results (Figure 9) show thatthe ligand was found to posses more antibacterial activitythan the complexes against different bacteria The increasein biological activity of the metal complexes than the ligandsmay be due to complexation and it can be explained on thebasis of chelation theory [38]


4 Conclusion

The CoII and NiII complexes are found to be octahedral andCuII complexes distorted-octahedral ZnII CdII and HgIIcomplexes are assigned to have tetrahedral geometry Boththe azo dyes behave as dibasic tetradentate ligands coor-dinating through oxine nitrogen phenolic oxygen enolicoxygen and amidic oxygen atoms All the complexes aredimeric in nature The complexes are found to be thermallystable From the thermal study of the complexes the orderof decomposition reaction activation energy and correlationcoefficients has been calculated The XRD study indicates amonoclinic crystal system for both the CoII complexes Allcalculations based onmolecular mechanics on the optimizedgeometries fit well with the experimental findings The crys-tallite sizes of the complex compounds have been determinedThe potential antibacterial study of the ligands as well as CoIINiII CuII and ZnII complexes has been made against grampositive and gram negative bacteria which gives encouragingresults

Acknowledgments

Theauthors are thankful toTheHead SAIF and IITMadrasIndia for providing spectral analysis MMIT Bhubaneswarfor kind help of XRD data and Dr J Panda Departmentof Microbiology Roland Institute of Pharmacy BerhampurOdisha India for providing antibacterial data

References

[1] L S Goodman and A Gilman The Pharmacological Basis ofTherapenticsMacmillan NewYork NYUSA 4th edition 1970

[2] K N Gaind and JM Khanna Indian Journal of PharmaceuticalSciences vol 26 p 34 1949

[3] R M Isa A K Ghoneium H A Dessouki andMMMustafaldquoCo(II) Ni(II) and Cu(II) complexes of some phenylazosalisy-laldehyde derivativesrdquo Journal of the Indian Chemical Societyvol 61 pp 286ndash289 1984

[4] B B Mahapatra R R Mishra and A K Sarangi ldquoSynthe-sis characterisation XRD molecular modelling and potentialantibacterial studies of Co(II) Ni(II) Cu(II) Zn(II) Cd(II)and Hg(II) complexes with bidentate azodye ligandrdquo Journal ofSaudi Chemical Society 2013

[5] B B Mahapatra and S K Panda ldquoCoordination compoundsof CoII NiII CuII ZnII CdII and HgII with tridentate ONSdonor azo dye ligandsrdquoBiokemistri vol 22 no 2 pp 71ndash75 2011

[6] B B Mahapatra and S K Panda ldquoPolymetallic complexesrdquoIndian Journal of Chemistry vol 87 pp 1447ndash1452 2010

[7] B BMahapatra and S K Panda ldquoPolymetallic complexes Part-XCIX tetrameric and dimeric CoII NiII CuII ZnII CdII andHgII complexes with hexa- and tetradentate azodye ligandsrdquoIndian Journal of Chemistry vol 87 pp 1199ndash1204 2010

[8] B B Mahapatra A K Sarangi S K Panda et al ldquoPolymetalliccomplexes part C dimeric Co(II) Ni(II) Cu(II) Zn(II) Cd(II)and Hg(II) complexes with bis-bidentate azodye ligandsrdquo JtrChemicals Corporation vol 16 no 2 pp 59ndash63 2009

[9] B B Mahapatra and A K Sarangi ldquoPolymetallic complexesPart-LXIV hexadentateOONndashNOOdonor azodye tetrameric

complexes of CoII NiII CuII ZnII CdII and HgIIrdquo Journal ofthe Indian Chemical Society vol 86 pp 559ndash563 2009

[10] R S Brandt and E R Miller ldquoStudies with the agar cup-platemethod I A standardized agar cup-plate techniquerdquo Journal ofBacteriology vol 38 no 5 pp 525ndash537 1939

[11] J V Quagliano J Fujita G Franz D J Phillips J A Walmsleyand S Y Tyree ldquoThe donor properties of pyridine N-oxiderdquoJournal of the American Chemical Society vol 83 no 18 pp3770ndash3773 1961

[12] F A Cotton and P G Wilkinson Advanced Inorganic Chem-istry Wiley Eastern New Delhi India 3rd edition 1985

[13] L K Mishra and B K Keshari ldquoThiohydrazides as complexingagent part 1-complexes of Ni(II) Co(II amp III) Cu(II) Zn(II)Cd(II) Pd(II) amp Hg(II) with O-HydroxyphenylthiohydraziderdquoIndian Journal of Chemistry A vol 28 pp 883ndash887 1981

[14] P B Dorian H H Patterson and P C Jordan ldquoOptical spectraof Os4+ in single cubic crystals at 42∘Krdquo Journal of ChemicalPhysics vol 49 no 9 p 3845 1968

[15] R Magee and L Gordan ldquoThe infrared spectra of chelatecompounds-I a study of some metal chelate compounds of 8-hydroxyquinoline in the region 625 to 5000 cmminus1 rdquo Talanta vol10 no 8 pp 851ndash859 1963

[16] R K Bajaj G S Sodhi and N K Kashia ldquoHalide andcomplex halogeno anions as salts of oxinato bis(1205785-indenyl)titanium(IV)zirconium(IV) chelatesrdquo Polyhedron vol 3 no 7pp 883ndash887 1984

[17] G S Sodhi A K Sharma and N K Kaushik ldquoHalideand complex halogeno anions as salts of oxinate chelates oftitanium(IV)rdquo Journal of Organometallic Chemistry vol 238no 2 pp 177ndash183 1982

[18] K Nakamoto Infrared Spectra of Inorganic and Co-OrdinationCompounds Wiley Interscience New York NY USA 1983

[19] J R Ferraro Low Frequency Vibration of Inorganic and Coordi-nation Compounds Plenum Press New York NY USA 1971

[20] A B P Lever Electronic Spectroscopy Elsevier AmsterdamTheNetherlands 1968

[21] A B P Lever ldquoThe electronic spectra of tetragonal metalcomplexes analysis and significancerdquo Coordination ChemistryReviews vol 3 no 2 pp 119ndash140 1968

[22] C R Hare and C J Ballahusen ldquoCrystal spectrum andmagnetism of Tetrakis-Thiourea-Nickel Chloriderdquo Journal ofChemical Physics vol 40 p 788 1984

[23] S Yamada ldquoRecent aspects of the stereochemistry of schiff-base-metal complexesrdquo Coordination Chemistry Reviews vol 1no 4 pp 415ndash437 1966

[24] CK Jorgensen ldquoComparative crystal field studies II Nickel(II)and copper(II) complexes with polydentate ligands and thebehaviour of the residual places for co-ordinationrdquo Acta Chem-ica Scandinavica vol 10 pp 887ndash910 1966

[25] DHWilliams and I Fleming SpectroscopicMethods inOrganicChemisty Tata McGraw-Hill Chennai India 4th Edn edition1994

[26] F K Kneubuhl ldquoLine shapes of electron paramagnetic res-onance signals produced by powders glasses and viscousliquidsrdquo Journal of Chemical Physics vol 33 p 1074 1960

[27] J M Visser ldquoA fully automated programme for finding the unitcell from power datardquo Journal of Applied Crystallography vol 2no 3 pp 89ndash95 1969

[28] P M De Woulff ldquoA simplified criterion for the reliability of apowder pattern indexingrdquo Journal of Applied Crystallographyvol 1 pp 108ndash113 1968


[29] A Patterson ldquoThe Scherrer formula for X-ray particle sizedeterminationrdquo Physical Review vol 56 no 10 pp 978ndash9821939

[30] AAbu-Hussen ldquoSynthesis and spectroscopic studies on ternarybis-Schiff-base complexes having oxygen andor nitrogendonorsrdquo Journal of Coordination Chemistry vol 59 no 2 pp157ndash176 2006

[31] E S Freeman and B Carrol ldquoThe application of thermoana-lytical techniques to reaction kinetics the thermogravimetricevaluation of the kinetics of the decomposition of calciumoxalatemonohydraterdquo Journal of Physical Chemistry vol 62 no4 pp 394ndash397 1958

[32] AM El-Award ldquoCatalytic effect of some chromites on the ther-mal decomposition of KClO

4 Mechanistic and non-isothermal

kinetic studiesrdquo Journal of Thermal Analysis and Calorimetryvol 61 p 197 2000

[33] A Impura Y Inoue and I Yasumori ldquoCatalysis by ldquoCop-per Chromiterdquo I The effect of hydrogen reduction on thecomposition structure and catalytic activity for methanoldecompositionrdquo Bulletin of the Chemical Society of Japan vol56 no 8 pp 2203ndash2207 1983

[34] M AThomson andM C Zerner ldquoA theoretical examination ofthe electronic structure and spectroscopy of the photosyntheticreaction center fromRhodopseudomonas viridisrdquo Journal of theAmerican Chemical Society vol 113 no 22 pp 8210ndash8215 1991

[35] A K Rappe and W A Goddard III ldquoCharge equilibration formolecular dynamics simulationsrdquo Journal of Physical Chemistryvol 95 no 8 pp 3358ndash3363 1991

[36] A K Rappe K S Colwel and J Cassewit ldquoApplication of auniversal force field to metal complexesrdquo Journal of InorganicChemistry vol 32 no 16 pp 3438ndash3450 1993

[37] J Cassewit K S Colwel and A K Rappe ldquoApplication of auniversal force field to main group compoundsrdquo Journal of theAmerican Chemical Society vol 114 no 25 pp 10046ndash100531992

[38] K Mahanan and S N Devi ldquoSynthesis characterization ther-mal stability reactivity and antimicrobial properties of somenovel lanthanide(III) complexes of 2-(N-salicylideneamino)-3-carboxyethyl-4567- tetrahydrobenzo[b]thiophenerdquo RussianJournal of CoordinationChemistry vol 32 p 600 2006

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Table 1 Analytical and physical data of the ligands and its complexes

Compounds Meltingpoint (∘C) Colour Metal found

(calculated) Nitrogen found

(calculated) Chlorine found

(calculated) 120583eff BM

LH2 110 Dark brown mdash 1456 (1500) mdashL1015840H2 85 Orange red 1300 (1341)[Co2LCl2(H2O)6] gt280 Brown 1326 (1378) 952 (983) 800 (831) 50[Co2L

1015840Cl2(H2O)6] gt280 Greenish yellow 1233 (1279) 86 (912) 725 (771) 51[Ni2LCl2(H2O)6] gt280 Brown 1319 (1374) 933 (983) 795 (831) 31[Ni2L

1015840Cl2(H2O)6] gt280 Brown 1230 (1275) 890 (913) 726 (771) 30[Cu2LCl2(H2O)6] gt280 Dark brown 1464 (1469) 966 (974) 791 (822) 18[Cu2L

1015840Cl2(H2O)6] gt280 Orange red 1361 (1365) 889 (903) 712 (763) 18[Zn2LCl2(H2O)2] gt280 Light brown 1600 (1643) 1017 (1055) 844 (892) mdash[Zn2L

1015840Cl2(H2O)2] gt280 Light brown 1483 (1517) 957 (975) 783 (823)[Cd2LCl2(H2O)2] gt280 Light brown 2495 (2426) 905 (944) 740 (798) mdash[Cd2L

1015840Cl2(H2O)2] gt280 Light brown 2301 (2352) 832 (879) 694 (743)[Hg2LCl2(H2O)2] gt280 Brown 3731 (3763) 723 (788) 607 (666) mdash[Hg2L

1015840Cl2(H2O)2] gt280 Buff 3501 (3543) 700 (742) 582 (627)LH2 = 441015840-bis(41015840-hydroxyquinolinolinylazo)diphenylsulphoneL1015840H2 = 441015840-bis(acetoacetanilideazo)diphenylsulphone

23 Synthesis of Metal Complexes The metal chlorides inethanol were mixed separately with ethanolic solution of theligands in 2 1 molar ratio and the resulting solutions wereheated to 60ndash70∘C for about one hour on a heating mantleThe solution was then cooled down to room temperature andthe pH was raised to sim7 by adding conc ammonia drop bydrop with stirring The solid complexes thus separated werethen washed with ethanol followed by ether and dried invacuum

24 Physical Measurements The elemental analysis (CH N)were carried out on elemental analyser Perkin-Elmer 2400while metals were determined by EDTA after decompos-ing the complexes with conc HNO

3 Conductance mea-

surements of the complexes were made using ToshniwalCL 01ndash06 Conductivity Bridge The magnetic susceptibilitywere made at RT by Gouy method using Hg[Co(CN)

4] as

calibrant IR spectra (KBr) were recorded using IFS 66Uspectrophotometer electronic spectra of the CoII NiII andCuII complexes in DMF were recorded on a Hilger-Wattuvispeck spectrophotometer ESR spectra of CuII complexwere recorded on a E

4-spectrometer and NMR spectra were

recorded on a Jeol GSX 400 with DMSO as solvent and TMSas internal standard X-ray diffraction (powder pattern) ofthe CoII complexes was recorded on a Phillips PW 113000diffractometer and the TG DTG and DTA of the complexeswere recorded on NETZSCH STA 409 CCD in nitrogenatmosphere at a heating rate of 10∘C per minute

25 Molecular Modelling Molecular modelling of the ligandand complexes has been made by Argus Lab 401

26 Antibacterial Activity The antibacterial activity of theazodye ligands and CoII NiII CuII and ZnII complexes were

studied as per cup-plate method [10] using two strains ofbacteria like Staphylococcus aureus and E coli The solutionsof the test compounds are prepared in dimethylsulfoxide(DMSO) at 500 120583gmL The bacterial strains are inoculatedinto 100mL of the sterile nutrient broth and incubated at37 plusmn 1

∘C for 24 hoursThe density of the bacterial suspensionis standardized by McFarland method A well of uniformdiameter (6mm) is made on agar plates after inoculatingthem separately with the test organisms aseptically Thestandard drug and the test compounds are introduced withthe help of micropipette and the plates are placed in therefrigerator at 8ndash10∘C for proper diffusion of drug into themedia After two hours of cold incubation the petri platesare transferred to incubator and maintained at 37 plusmn 2

∘C for18ndash24 hours Then the petri plates are observed for zone ofinhibition by using vernier scale The results are reportedby comparing the zone of inhibition shown by the testcompounds with standard drug tetracycline The results arethe mean value of zone of inhibition of three sets measuredin millimetre

3 Results and Discussion

The physical characteristics and microanalytical data ofthe ligands and the complexes are given in (Table 1) Theanalytical data of the complexes revealed 2 1 molar ratio(metal ligand) which corresponds well with the generalformula [M

2LL1015840Cl

2(H2O)6] and [M1015840

2LL1015840Cl

2(H2O)2] where

M = CoII NiII CuII M1015840 = ZnII CdII HgII LH2= 441015840-bis

(41015840-hydroxyquinolinylazo)diphenylsulphone C30H20N6O4S

(Calcd () C 6428 H 36 N 1499 Found () C 638H 33 N 145) L1015840H

2= 441015840-bis(acetoacetalidoazo)diphen-

ylsulphone C32H30N6O6S (Calculated () C 6133 H 483

N 1341 Found () C 611 H 46 N 132) All the complexes




1015840Cl2(H2O)6] 1240 1648 514 460[Ni2LCl2(H2O)6] 1135 1325 510 452[Ni2L

1015840Cl2(H2O)6] 1243 1645 513 455[Cu2LCl2(H2O)6] 1135 1330 510 450[Cu2L

1015840Cl2(H2O)6] 1233 1643 512 458[Zn2LCl2(H2O)2] 1134 1325 508 452[Zn2L

1015840Cl2(H2O)2] 1235 1645 511 457[Cd2LCl2(H2O)2] 1133 1324 510 450[Cd2L

1015840Cl2(H2O)2] 1240 1640 514 455[Hg2LCl2(H2O)2] 1135 1330 508 452[Hg2L

1015840Cl2(H2O)2] 1245 1642 510 460



2) and at




2) can be













1)


4T1g (P) (]



35= 0790(0804) cmminus1 ]

2]1


2g (F) rarr3T2g (F) (]1)




= 0730(0748) cmminus1 ]2]1= 1673(1688) and 120590 =


2T2g








2corresponds




3) pro-





gav = 2(1 minus 2120582

10Dq) (1)




2L1015840Cl2(H2O)6]





119899 =119889119873119881

119872 (2)


119861 =119896120582

119904 sdot cos 120579 (3)





Name May 29-201241

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

01234567891011121314(ppm)

100 3

209

910

340

1354

10

276

59

90

007


650 120583s48400 120583s

1065 120583s

(a)

01234567891011121314

100

098

034

230

036

036

420

077

244

117

111

070

057

088

(ppm)



Name May 29-201231

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

650 120583s48400 120583s

1065 120583s

(b)


2


(a)

(b)



0 20 40 60 80 1002120579

0

2

4

6

8

Inte

nsity

(am

u)

Powder XRD

(a)

0 20 40 60 80 1002120579

0

10

20

30

40

50

60

Inte

nsity

(b)




(a) (b)

(c)









2O molecules





2LCl2(H2O)6]








(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1015840Cl2(H2O)6] 1240 1648 514 460[Ni2LCl2(H2O)6] 1135 1325 510 452[Ni2L

1015840Cl2(H2O)6] 1243 1645 513 455[Cu2LCl2(H2O)6] 1135 1330 510 450[Cu2L

1015840Cl2(H2O)6] 1233 1643 512 458[Zn2LCl2(H2O)2] 1134 1325 508 452[Zn2L

1015840Cl2(H2O)2] 1235 1645 511 457[Cd2LCl2(H2O)2] 1133 1324 510 450[Cd2L

1015840Cl2(H2O)2] 1240 1640 514 455[Hg2LCl2(H2O)2] 1135 1330 508 452[Hg2L

1015840Cl2(H2O)2] 1245 1642 510 460



2) and at




2) can be













1)


4T1g (P) (]



35= 0790(0804) cmminus1 ]

2]1


2g (F) rarr3T2g (F) (]1)




= 0730(0748) cmminus1 ]2]1= 1673(1688) and 120590 =


2T2g








2corresponds




3) pro-





gav = 2(1 minus 2120582

10Dq) (1)




2L1015840Cl2(H2O)6]





119899 =119889119873119881

119872 (2)


119861 =119896120582

119904 sdot cos 120579 (3)





Name May 29-201241

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

01234567891011121314(ppm)

100 3

209

910

340

1354

10

276

59

90

007


650 120583s48400 120583s

1065 120583s

(a)

01234567891011121314

100

098

034

230

036

036

420

077

244

117

111

070

057

088

(ppm)



Name May 29-201231

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

650 120583s48400 120583s

1065 120583s

(b)


2


(a)

(b)



0 20 40 60 80 1002120579

0

2

4

6

8

Inte

nsity

(am

u)

Powder XRD

(a)

0 20 40 60 80 1002120579

0

10

20

30

40

50

60

Inte

nsity

(b)




(a) (b)

(c)









2O molecules





2LCl2(H2O)6]








(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







2corresponds




3) pro-





gav = 2(1 minus 2120582

10Dq) (1)




2L1015840Cl2(H2O)6]





119899 =119889119873119881

119872 (2)


119861 =119896120582

119904 sdot cos 120579 (3)





Name May 29-201241

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

01234567891011121314(ppm)

100 3

209

910

340

1354

10

276

59

90

007


650 120583s48400 120583s

1065 120583s

(a)

01234567891011121314

100

098

034

230

036

036

420

077

244

117

111

070

057

088

(ppm)



Name May 29-201231

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

650 120583s48400 120583s

1065 120583s

(b)


2


(a)

(b)



0 20 40 60 80 1002120579

0

2

4

6

8

Inte

nsity

(am

u)

Powder XRD

(a)

0 20 40 60 80 1002120579

0

10

20

30

40

50

60

Inte

nsity

(b)




(a) (b)

(c)









2O molecules





2LCl2(H2O)6]








(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Name May 29-201241

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

01234567891011121314(ppm)

100 3

209

910

340

1354

10

276

59

90

007


650 120583s48400 120583s

1065 120583s

(a)

01234567891011121314

100

098

034

230

036

036

420

077

244

117

111

070

057

088

(ppm)



Name May 29-201231

EXPNOPROCNO


10330578 Hz

15860212 s203

100000000 s1

Channel f1


EM

650 120583s48400 120583s

1065 120583s

(b)


2


(a)

(b)



0 20 40 60 80 1002120579

0

2

4

6

8

Inte

nsity

(am

u)

Powder XRD

(a)

0 20 40 60 80 1002120579

0

10

20

30

40

50

60

Inte

nsity

(b)




(a) (b)

(c)









2O molecules





2LCl2(H2O)6]








(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a)

(b)



0 20 40 60 80 1002120579

0

2

4

6

8

Inte

nsity

(am

u)

Powder XRD

(a)

0 20 40 60 80 1002120579

0

10

20

30

40

50

60

Inte

nsity

(b)




(a) (b)

(c)









2O molecules





2LCl2(H2O)6]








(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a) (b)

(c)









2O molecules





2LCl2(H2O)6]








(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





(a)


(b)


(c)


(d)


(e)


(e) Continued


(f)


(g)


(h)



1015840Cl2(H2O)6]

(a)


(b)



Complex 119899 (119864119886) in 119869mole 119903

[Co2L1015840Cl2(H2O)6] 069 8229 088

[Ni2LCl2(H2O)6] 062 7655 098[Ni2L

1015840Cl2(H2O)6] 12 34639 087










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










2L1015840Cl2(H2O)6]


minus119889119908

119889119905= 119877119879=

119885

119877119867119890minus119864119886119877119879 sdot 119882119899

(4)






2) (L1015840H




0

10

20

30

40

Zone

of i

nhib

ition

(mm

)

Compound1 2 3 4 5 6 7 8 9 10 11





4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


4 Conclusion


Acknowledgments


References




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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