Macap Fill 3009(20):Macap Fill 3009(20).qxd.qxd Polymetallic Complexes Part LXXXXI Dimeric and Monomeric Complexes of CoII, NiII, CuII, ZnII, CdII and HgII with N O-O N and N O Donor Bis-bidentate and Bi-dentate Azodye Ligands. Bi. B. Mahapatra* and A. K. Sarangi P.G. Department of Chemistry, G.M. Autonomous College, Sambalpur-768004, Orissa, India. Abstract Bis-bidentate azodye, 4,4 / -bis (4 / -dihydroxyquinolineazo)3,3 / -dimethoxydibenzene having N O-O N donors and bidentate azodye (4 -hyoxyquinolineazo)4 / -methoxybenzene having N O donors form dimeric and monomeric complexes of the type [M2LCl2(H2O)6], [M / 2LCl2(H2O)2], [ML / 2(H2O)2] and [M / L / 2] where M = Co II, NiII, CuII; M / = ZnII, CdII, HgII . The complexes of the first and third cat- egories are found to be six-coordinated with an octahedral and distorted octahedral configuration and the complexes of second and fourth type are four-coordinated with a tetrahedral geometry around the metal ions. The complexes have been characterised based upon analytical, conductance, magnetic susceptibility, i.r., electronic spectra, N.M.R., E.S.R. and X-ray diffraction data. The unit cell parameters like a, b, c, α, ß, γ and V (volume) have been calculated from the 2θ values. The unit cell geometry of the complex [Co2LCl2(H2O)6] is found to be monoclinic. Key words: Polymetallic complexes, Azodye complexes, Multidentate ligands. Introduction The pharmacological and chemotherapeutic activity of azodye is well recognised (Goodman and Gilman, 1970). Synthetic chemists have been inspired to prepare broad spec- trum drugs from the azodyes of aromatic and heterocyclic amines. Some of the azodyes are used for dyeing food stuffs, preserving food grains and as redox indicator (Isa et al.,). Potentiometric and Spectrophotometric studies of metal complexes with azodye ligands have been reported. Oxine and its derivatives possess antibacterial and amoebicidal properties (Porter et al., 1968). We have earlier reported the synthesis of a number of multidonor azodyes and their poly- meric metal complexes (Mahapatra et al., 1987). The present work reports the synthesis of one bis-bidentate and one bidentate azodye ligands containing these two potentional biologically active moieties and their twelve dinuclear and mononuclear metal complexes with CoII, NiII, CuII, ZnII, CdII and HgII ions. Bangladesh J. Sci. Ind. Res. 46(2), 259-264, 2011 BCSIR Available online at www.banglajol.info BANGLADESH JOURNAL OF SCIENTIFIC AND INDUSTRIAL RESEARCH E-mail: bjsir07@gmail.com * Corresponding author: E-mail: mahapatra.bipin@yahoo.com, ashishsbp_2008@yahoo.com [Fig. 1] [Fig. 2] Materials and Methods o-dianisidine, p-anisidine and 8-hydroxyquinoline are B.D.H. or E. Merck grade. Metal, nitrogen and chloride con- tents were estimated by standard methods. Conductivity measurement in DMF was made using Toshniwal CL 01-06 Conductivity Bridge. Magnetic moment was measured by Gouy method at room temperature. I.R. Spectra (KBr) were recorded on an IFS 66U Spectrophotometer, electronic spec- tra (10-2M in DMF) using Hilger-Watt uvispeck spectropho- tometer, E.S.R. spectrum on a E4- spectrometer and N.M.R. spectra on a Jeol GSX 400 with CDCl3 as solvent and rela- tive to tetramethylsilane and X-ray diffraction (powder pat- tern) of the complex [Co2LCl2 (H2O)6] was recorded on a Phillip PW 113/00 diffractometer. Preparation of 4,4 / -bis (4 / -hydroxyquinolineazo)3,3 / - dimethoxydibenzene o-dianisidine (0.01 mol, 2.44 g) was dissolved in dil. HCl (10 mL) and was kept in ice cold water (0-5oC). Sodium nitrite solution was then added to it slowly with stirring when the corresponding diazonium chloride was formed. To the 8-hydroxyquinoline (Oxime) (0.02 mol, 3.18 g) solution in ethanol, sodium hydroxide solution was added and the resulting solution was then poured in to the above diazonium chloride slowly with stirring when a red coloured azodye (LH2) separated out. It was then filtered, washed with water and dried in vacuo. Preparation of (4-hyoxyquinolineazo)4 / -methoxybenzene This azodye was prepared in a similar method by the cou- pling reaction of p-anisidine (0.01 mol, 1.23 g) with alkaline solution of 8-hydroxyquinoline (Oxine) (0.01 mol, 1.59 g). The reddish yellow azodye separated out immediately was then filtered, washed with water and dried in vacuo. Preparation of the complexes The metal chlorides in ethanol were mixed together with ethanolic solution of the ligands and the resulting solutions were refluxed at ~50 o C for an hour on a heating mantle. The solution was then cooled down to room temperature and the pH was raised to ~7 by adding conc. ammonia drop by drop with stirring. The solid complexes thus separated were then washed with ethanol, followed by ether and dried in vacuum. Result and Discussions The analytical data (Table I) indicate that the metal complex- es have the compositions [M2LCl2(H2O)6] , [M | 2LCl2 (H2O)2], [ML | 2 (H2O)2] and [M |L| 2]; where M = Co II , NiII, 260 Polymetallic Complexes Part 46(2) 2011 Compound Colour % Metal Found % Nitrogen Found % Chlorine Found μ eff B.M. (Calculated) (Calculated) (Calculated) LH2 Red - 14.87 (15.10) - - LlH Reddish yellow - 14.73 (15.04) - - [Co2LCl2 (H2O)6] Violet 13.58 (13.76) 9.65 (9.88) 8.12 (8.35) 5.1 [CoLl2(H2O)2] Red 8.83 (9.05) 12.71 (12.90) - 5.0 [Ni2LCl2 (H2O)6] Reddish brown 13.52 (13.76) 9.79 (9.88) 8.21 (8.35) 3.1 [NiLl2(H2O)2] Reddish brown 8.88 (9.01) 12.73 (12.90) - 3.0 [Cu2LCl2 (H2O)6] Light brown 14.4 (14.76) 9.54 (9.76) 8.13 (8.25) 1.8 [CuLl2(H2O)2] Light brown 9.43 (9.69) 12.67 (12.81) - 1.8 [Zn2LCl2 (H2O)2] Brown 16.19 (16.42) 10.46 (10.61) 8.75 (8.96) - [ZnL l2] Brown 10.28 (10.52) 13.23 (13.51) - - [Cd2LCl2 (H2O)2] Brown 25.13 (25.31) 9.27 (9.49) 7.84 (8.02) - [CdLl2] Dark brown 16.55 (16.76) 12.36 (12.57) - - [Hg2LCl2 (H2O)2] Reddish brown 37.41 (37.75) 7.72 (7.90) 6.35 (6.68) - [HgLl2] Reddish brown 26.38 (26.51) 10.96 (11.10) - - Table I: Analytical and Physical data of the complexes Mahapatra and Sarangi 261 CuII ; M = ZnII, CdII, HgII ; LH2 = C32 H24 O 4N6 (Fig. 1) (Calcd. (%) C, 69.06; H, 4.35; N, 15.1; Found (%) C, 69.02; H, 4.31; N, 14.87); L|H4= C16 H13 O2N3 (Fig. 2) (Calcd. (%) C, 68.81; H, 4.69; N, 15.04; Found (%) C, 68.63; H, 4.54; N, 14.73) . All the six complexes with ligand (LH2) are powdery in nature having high melting points and are insoluble in common organic solvents but the six complexes with ligand (L|H) are crystalline, soluble in organic solvents and have low melting points. The non-electrolytic nature of all the twelve complexes are correlated with the low M values (4.3- 6.5 Ω-1 cm2 mol-1). In the IR spectra of the ligands, (Table II) one broad band appears at 3431(LH2) and the other at 3411 (L IH) which might be due to O-H…N intramolecular hydrogen bonding. These bands are non-existent in the metal complexes, indi- cating the bonding of the phenolic -OH groups to the metal ions (Mishra and Keshari, 1981). The v (-N=N-) band observed at 1595 cm-1(LH2) and 1600 cm -1(LIH) remain unaffected in the metal chelates showing non-coordination of the azo nitrogen atoms to the metal atoms (King and Bisnette, 1966). The bands observed at 1168 cm-1 (LH2) and 1152 cm -1 (LIH) in the ligands are attributable to v (C-O) vibration and the bathochromic shift of ~ 40 cm-1 in the metal complexes indi- cates the bonding of oxine oxygen to the metal atom. In the spectra of the ligands, an intense band is observed at 1400 cm-1(LH2) and at 1403 cm -1(LIH) due to C---------- N Vibration of the oxinate (Magee and Gorden) group. In the metal com- plexes this band occurs at ~1320 cm-1. The shift of this band to lower frequency regions show considerably lower double bond character of the C---------- N bond due to involvement of the ring nitrogen on complexation. One broad band appears in the region 3400-3412 cm-1 for LH2 complexes and the other peaks at ~837-842 cm-1 for CoII , NiII and CuII , LIH complexes which are assignable to -OH stretching and rock- ing vibrations respectively indicating the presence of co- ordinated water molecules in the complexes (Nakamoto, 1978 and Gamo, 1961) .The evidence of bonding of oxy- gen and nitrogen atoms in oxine is further substantiated by the appearance (Ferraro, 1971) of bands at ~603 cm-1and ~516 cm-1 assignable to v (M-O) and v (M-N) vibrations respec- tively. The cobalt(II), nickel(II) and copper(II) complexes exhibit magnetic moments at ~ 5.1, 3.1 and 1.8 B.M. indicating the presence of three, two and one unpaired electron respective- ly (Cotton and Wilkinson, 1988) . Three bands appear at 9100(9090), 18315(18280) and 21560(21470) cm-1 in the electronic spectra of CoII complex- es, which could be attributed to 4T1g (F) �4T2g (F) (v1),� 4A2g (F) (v2) and�4T1g (P) (v3) transitions respectively. The value of the spectral parameters like Dq = 921.5(919) cm-1 , B = 838.3 (832.0) cm-1 , β35 = 0.863 (0.856) cm -1 , v 2/v 1 = 2.01(2.01) and σ = 15.87% (16.82%) of Co II com- plexes are suggestive of an octahedral stereochemistry around the metal ion (Lever 1968). In the electronic spectra of NiII complexes, four bands appear at 10250(10282), 17122(17315), 24980(24992) and 32240(31355) cm-1 which may be assigned to 3A2g(F)� 3T2g(F) (v1), � 3T1g(F) (v2), �3T1g(P) (v3) and CT transition respectively. Spectral parameters like Dq = 1025.0 (1028.2) cm-1, B = 756.80 (764.06) cm-1, β35 = 0.726 (0.773) cm -1, v2/ v1 = 1.67(1.68) and σ = 37.74% (36.42%) indicates the octahe- dral symmetry. In the case of the copper (II) complexes one broad asymmetry band appears at 12750-12980 cm-1charac- teristic of distorted octahedral stereochemistry with D4h sym- metry (Procter et al., 1968). The broadness of the bands might be due to Jahn-Teller distortion. Compounds v(C-O) v( C-------N ) v(M-O) v(M-N) LH2 1168 1400 - - LlH 1152 1403 - - [Co2LCl2 (H2O)6] 1130 1321 603 516 [CoLl 2(H2O)2] 1112 1313 603 517 [Ni2LCl2 (H2O)6] 1130 1321 602 515 [NiLl2(H2O)2] 1115 1315 602 516 [Cu2LCl2 (H2O)6] 1132 1320 603 515 [CuLl2(H2O)2] 1112 1313 603 517 [Zn2LCl2 (H2O)2] 1130 1322 603 516 [ZnLl2] 1115 1315 603 517 [Cd2LCl2 (H2O)2] 1130 1320 602 515 [CdLl2] 1110 1313 602 515 [Hg2LCl2 (H2O)2] 1132 1321 601 516 [HgLl2] 1115 1315 602 516 Table II: Infrared spectra of the ligands and the com- plexes 262 Polymetallic Complexes Part 46(2) 2011 In the E.S.R. spectra of the copper complexes [Cu2LCl2 (H2O)6] and [Cu2LI2(H2O)2] were recorded at Q-band and the 'gav' values were found to be 2.05554 and 2.05848 respectively by Kneubuhl's method (Kneubuhl 1960). These spectra are found to be isotropic, consisting of a single line which is a characteristic of complexes having regular octa- hedral geometry. This type of spectrum may also result due to regular octahedral stereochemistry undergoing a dynamic or pseudo-rotational type of Jahn-Teller distortion. The 1H NMR spectra of the ligands LH2 and L 1H were recorded in CDCl3 solvent with TMS as internal standard. The complex pattern observed at δ 6.797 -8.198 (LH2) and δ 6.983 - 8.186 (L1H) corresponds to 16 and 8 aromatic pro- tons each. The sharp singlet peak observed at δ 4.019 (LH2) and δ 3.972 (L1H) corresponds to six and three methoxy (-OCH3) protons respectively. The phenolic protons could not be detected as it was beyond the range of the instrument. The XRD study (powder pattern) of the complex [CO2LCl2 (H2O)6] was shown in graph-1. The unit cell parameters a, b, c, α, β, γ and V (volume) have been calculated from the 2θ values. The density (d) of the complex was determined by floatation method. The number of formula units (n) per unit cell is calculated from the relation n = dNV / M where d = density of the compound, N = Avogadro's number, V = Volume of the unit cell and M = molecular weight of the compound. The value of 'n' is found to be 1.0 for the com- plex corresponding to the volume of the unit cell 414.95 Å . The unit cell is found to be 'monoclinic', based upon the unit cell parameters (Puri et al, 1993) (Table III). The ZnII, CdII and HgII complexes are suggested to be four- coordinated having tetrahedral geometry based on analytical, IR and conductance data. Conclusion The azodye LH2 having O N-N O donor atoms behaves as a bis-bidentate ligand and the azodye L/H behaves as a biden- tate ligand having O N donor atoms. The former ligand binds two metal atoms on either side forming dimeric complexes whereas the latter ligand forms monomeric complexes with the metal ions. Both the azodyes coordinate to the metal atoms through the quinolyl oxygen and nitrogen atoms. Graph-1: XRD Graph for [Co2LCl2 (H2O) 6] complex Mahapatra and Sarangi 263 Acknowledgement The authors wish to thank Sri L.D. Pradhan, Scientist, R.R.L. Bhubaneswar (Orissa) for his kind help in recording and analysing the XRD spectrum of the CoII complex. References Cotton F. A. and Wilkinson P. G. (1988). Advanced Inorganic Chemistry. 5th Ed. (John Wiley & Sons, NY, USA). Dessouki H. A., Issa R. M., Ghoneium A. K. and Moustafa M. M. (1984). Co(II), Ni(II) and Cu(II) Complexes of Some Phenylazosalisylaldehyde Derivatives. J. Indian Chem. Soc; 61: 286-289. Ferraro J. R. (1971). Low Frequency Vibration of Inorganic and Co-ordination Compound, (Plenum Press, NY, USA). Gamo I. (1961). Infrared Spectra of Water of Crystallization in Some Inorganic Chlorides and Sulfates. Bull. Chem. Soc., Jpn , 34: 760-764. Goodman L. S. and Gilman A. (1970). The Pharmacological Basis of Therapeutics, 4th Ed. (MacMillan, NY, USA). King R. B. and Bisnette M. B. (1966). 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Cobalt(II), nickel(II), c u p p e r ( I I ) , zinc(II), cadmium(II) and mercury(II), complexes with a chelating azodye ligand, 5-(o- hydroxyphenyldia- zo)-acetoacetanilide. Acta Chim, Hung, 24(3): 387- 390. Mahapatra B. B. and Saraf S. K. (2003). Polymetallic Complexes. Part-LXXXII. Bis-bidentate and Bis-tri- dentate Azodye Dimeric Complexes of CoII, NiII, CuII, ZnII, CdII and HgII. J. Indian Chem. Soc, 80: 696-699. Compound [Co2LCl2 (H2O)6] 10.897,12.991,14.935, 16.430,18.975,21.964, 28.993,32.300,39.313, 39.462,39.521,39.612, 50.137,53.670,53.820, 60.101,60.998,61.148, 68.626,73.411,73.860, 78.197,83.881,84.030, 85.675,88.218,89.265 a = 11.843 Å b = 4.925 Å c = 7.127 Å α = 90.00 O β = 93.425 O γ = 90.00 O V = 414.95 cc 2.04 1.0 Monoclinic 2θ -Values in degrees Unit cell parameters Density, (g/cm3) N Possible crystal system Table III: X-ray diffraction data of the complex 264 Polymetallic Complexes Part 46(2) 2011 Mishra L. K. and Keshari B. N. (1981). 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