Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 2(6), 43-49, June (2012) Res.J.Chem.Sci. International Science Congress Association 43 Synthesis and Structural Studies on Some Transition metal complexes of Bis-(benzimidazole-2-thio) ethane, propane and butane ligandsButtrus H. Nabeel* and Saeed T. Farah Department of Chemistry, College of Science, University of Mosul, Mosul, IRAQAvailable online at: www.isca.in (Received 18th March 2012, revised 29th March 2012, accepted 5th April 2012)Abstract Transition metal complexes of Co(II),Ni(II),Cu(II) and Zn(II) with the tetradentate ligands [L= 1,2-bis-(benzimidazole-2-thio) ethane, L=1,3-bis-(benzimidazole-2-thio) propane, L=1, 4-bis-(benzimidazole-2-thio)butane], derived from the condensation of 2-mercaptobenzimidazole and 1,2-dibromoethane or 1, 3-dibromo propane or 1, 4-dibromobutane were synthesized. Characterization has been done on the basis of analytical conductance, magnetic data, infrared, electronic spectra , metal content analysis and HNMR data for the ligands. From analytical data the stoichiometry of the complexes has been found to be (1:1) (metal: ligand). IR spectra data suggest that the ligands behave as bidentate with N,N or S,S or S,S,N,N donor sequence toward the metal ions. On the basis of the above spectral, physicochemal, data as well as magnetic moment measurements tetrahedral and square planner geometries were assigned for the complexes. Keywords: Metal complexes, benzimidazole-2-thio derivatives, spectral study. Introduction Interest in coordination chemistry is increasing continuously with the preparation of organic ligands containing a variety of donor groups1-2 and it is multiplied many fold when the ligand have biological importance3-4. Benzoimidazoles are involved in a great variety of biological processes. Some of their poly functional derivatives have been proven to possess antibacterial, fungicide and anti-hermitic activity5-8. Therefore substituted benzimidazoles have attracted the interest of various research group, especially since it has been reported that the influence of the substitution at 1,2 and 5-positions is very important for their pharmacological effect. Several groups have reported cobalt (II) and Zn(II) coordination compounds showing a similar stoichiometry [M(bz)] (MII=Co, Zn, X=Cl,Br,I; bz=benzimidazole)10-13. In all cases, the geometry adopted by the metal ion is tetrahedral. The compound dichloro bis (1H-benzimidazole)-cobalt(II) reported elsewhere10 is a type of the above complexes. Coordination compounds containing thiabendazole, 2-(4'-thiazolyl) benzimi-dazole form bis-chelate and tris-chelate compounds14. In all cases the ligand coordinates to the metal (cobalt (II), nickel (II),cupper(II) zinc(II), cadmium (II) and mercury (II) through the imidazolic and thiazolic nitrogen atoms. The spiracylic structure [Co(btz-SMe)], Btz=N-benzo-thiazole-2-yl) dithiocarbamic methyl ester, the ligand is derivative of benzothiazole, is anionic and behaves as bidentate, nitrogen and sulfur atoms are bonded to the central metal ion giving planar tricyclie chelates, where Co(II) is part of the six-membered rings15. The crystal structures of Co(II) and Ni(II) complexes of 4- (benzimidazole-2-yl)-3-thiabutanioc acid which provide a benzimidazole, a thioether and carboxyl donor group. The crystal structure of Cu(II) complex indicates that the two oxygen and two nitrogen donors for a square coordination around the copper ion, while the two sulfur are approximately axial to the copper center16. In view of the reported interesting results and in continuation of our studies on transition metal complexes with sulphur ,oxygen and nitrogen containing ligands 17-19, we are presenting here the preparation of new ligands 1,2 or 1,3 and 1,4-(benzimidazole-2-thio) ethane (L) ,propane (L) and butane (L) Scheme-1 and their Co(II), Ni(II),Cu(II) and Zn(II) complexes. Material and Methods All chemical were of reagent grade, were used as supplied (Fluka) or (B.D.H). Elemental analyses (C.H.N and S) were carried out using micro analytical techniques on Perkin Elmer 2400 (IEES) at AL-AL-bayt University (Jordon). Metal estimation were done on PYE UNICAM SPg atomic absorption spectro-photometer. The chloride was determined using the method in Vogel20. Conductivity measure- ements for 10-3M solution of the complexes in (DMF) were carried out with on Jenway 4070 conductivity meter and a dip cell with platinized electrode. Infrared spectra were recorded on a FTIR Brucker Tensor 27co spectrophotometer in the 200-4000 cm-1 range using CsI discs. The UV/Vis spectra were recorded on a Shimadzu UV-160 spectrophoto- meter for 10-3M solution of complexes in DMF using 1 cm quartz cell. Melting point were measured using an electrothermal 9300 digital melting point apparatus. Magnetic susceptibility was measured on the solid state by Faraday’s method using Brucker BM6 instrument at 25°C. all magnetic susceptibilities values were corrected for diamagnetic contribution using Pascal's constant. 1HNMR spectra of the ligands were carried on varian 300 MHz NMR spectrometer. Chemical shifts are reported in ppm relative to an internal standard of TMS. Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 43-49, June (2012) Res.J.Chem.SciInternational Science Congress Association 44 General procedure for the synthesis of the ligands (Schem-1): 1, 2-bis-(benzimidazole-2-thio)ethane (L): 1,2-dibromo ethane (1.88g,1mmol) in ethanol (10ml) was boiled under reflux for 6hr. with an equivalent a mount of 2-mercapto-benzimidazole (3.00g,2mmol) and NaOH (0.80g,2mmol)in ethanol (20 ml) , after cooling to room temperature, NaBr was removed by filtration. The resulting solution was reduced in volume to ca 1/3 , on cooling left a white solid. The solid thus obtained was filtered off , washed with ethanol and diethylether then dried under vacuum for several hours. 1,3-bis-(benzimidazole-2thio)propane (L) and 1,4-bis(benzimidazole-2-thio) butane (L) : These ligands were papered by using similar procedure as above except using 1,3-dibromopropane (2.02g,0.01mol) in case of (L) or (2.16g,0.01 mol) of 1,4-dibromobutane in case of (L). General procedure for the synthesis metal complexes (Schem-2): A clear solution of the ligand 1,2-bis (benzimidazole-2-thio)ethane (3.26g , 0.01 mol) in ethanol (20ml) was added to a solution of CoCl.6HO or NiCl.6HO or CuCl.2HO or ZnCl (1.0 mmol) in (10ml) ethanol, the reaction mixture was refluxed for 2 hours. Then the mixture was left for 24 hours, at room temperature to give the precipitate which was filtered off, washed with ethanol and diethylether, then dried under vacuum for 4 hours.SH + 2NaOH NHN S CH___CH NNH S NHN S CH_CH_CH NNH S NHN S CH_CH_CH_CH NNH S BrCHCHBrBrCHCHCHBrBrCHCHCHCHBr(L(L(L Scheme -1 Table-1 Physical properties of ligands Ligand no. Chemical formula Color m.p. Analysis found (calc.) % Selected IR Band max. max) nm Yield % C H N S (C=N) (C-S) C1614 white 256 58.57 (58.87) 5.27 (4.28) 17.59 (17.15) 20.07 (19.54) 1589, 1637 S 744 312 92 C1716 white 231 59.98 (59.97) 5.53 (4.69) 16.54 (16.44) 19.30 (18.83) 1655 742 314 89 C18 white 27561.11 (60.94) 5.98 (5.07) 15.32 (15.79) 18.48 (18.09) 1588 746 306 93 d=decomposition, S= strong, m=medium Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 43-49, June (2012) Res.J.Chem.SciInternational Science Congress Association 45 Results and DiscussionThe new tetradentate ligands (L),(L) and (L) were prepared by the reaction of 2-mercaptobenzimidazole with 1,2-dibromo-ethane or 1,3- dibromopropane or 1,4 dibromobutane to give 1,2 or 1,3 or 1,4 –bis (benzimidazole-2-thio) ethane or propane or butane in high yield table 1. The complexes were prepared through direct reaction of the metal chlorides, CoCl.6HO or NiCl.6HO or CuCl. 2HO or ZnCl with the above ligands in (1:1) molar ratio. All the metal complexes except Zn(II) complexes are colored, all of them are stable toward air and moisture. The metal complexes are insoluble in common organic solvents like chloroform, carbon tetrachloride, hexane, methanol, acetone. They are soluble in DMF or DMSO. The analytical data table-2 of the metal complexes show that all the metal chelates have 1:1 metal to ligand stoichiometry. Conductance measurements were carried out to ascertain the electrolytic/ non electrolytic nature of metal complexes, molar conductance values of complexes in 10-3M DMF solution at room temperature suggest the non electrolytic nature for complexes (1-8) and (1:2) electrolytic nature for the complexes (9-12) 21. HNMR data: The HNMR spectrum of the ligands (L),(L) and (L) were recorded in DMF-d7 solution. The results showed that the position of 11.83-12.47 NH protons (S,2H of benzimidazole), a multiple at 6.95- 7.25 due to aromatic protons and 1.63-3.75 for alkyl protons. For (L) 12.47 NH protons (S,2H, of benzimidazole), a multiplet at 7.09 – 7.52 (8H) due to aromatic protons, 3.75 (d,4H,S-CH), where as for (L) 12.47 NH protons (S,2H of benzimidazole) , a multiplet at 7.11- 7.44 (8H) is due to aromatic protons, 1.90 (S,2H,CH) and 2.19,4H,SCH) while for L11.86 NH protons (S,2H, of benzimidazole), a multiple at 7.11- 7.58 (8H) is due to aromatic protons, 1.63 (m, 4H and 2.11, 4H,SCH). The HNMR signals are in correlation with the expected structure scheme-1 Infrared spectral studies: The infrared spectrum of the free ligands shows strong band in the region 3330-3390 cm-1 which is assignable NH of benzimidazole ring. Strong bands located at 1578-1589, 1637-1655 and 742-746 cm-1 can be assigned to (C=N) and (C-S) respectively. A negative and positive shift in (C=N) to extent of (11-23) or (10-18) cm-1 in the spectra of the chelates suggest the involvement of azomethine nitrogen benzimidazole ring in coordination22 (figure 1, 2 and 3). Further support for this argument came from the IR of the complexes which showed new a bands at 480-499cm-1attributed to (M-N). They also showed a band in the region 300-330 cm-1 which may be due to (M-Cl) vibration frequency 23,24. The (C-S) band in the some complexes was shifted to lower frequency values, while other complexes was shifted upward table-3. Further support for this coordination has been provided by the appearance of new bands in the 360- 380 cm-1 ranges which are relatively attributed to (M-S)25,26. Magnetic Susceptibility measurements: The magnetic moments are measured at 25°C. The magnetic moments are (4.38-5.08) B.M for Co(II) complexes (1,5 and 9) respectively, while for Ni(II) complexes (2,6 and 10) are diamagnetic , for Cu(II) complexes (3,7 and 11) are (1.53-2.23) B.M. Suggest the presence of one unpaired electron, Zn(II) complexes (4,8,12) are diamagnetic. As the magnetic moment correlate very well with the mononuclear complexes. Electronic spectral studies: The UV-Visible spectra of the ligands and their complexes in 10-3 M solution DMF were recorded, the results were listed in Table-3, the bands observed at 306-314 nm were due to * or n- * transition within the ligandsThe spectrum of cobalt (II) complexes (1,5 and 9) show a bands at (610-690)nm. This band is assigned to g g (p) transition, which is consistent with proposed tetrahedral symmetry of these complexes. Further the blue colors of these complexes support its proposed tetrahedral geometry27. The diamagnetic nature of nickel (II) complexes (2,6 and 8) and the appearance of the bands at (574-678) and (408-430) nm were assigned to g g and g g transition in a square planner environment around nickel ion1728. The electronic spectra of Cu(II) complexes (3,7 and 11) showed a band at (810-848) nm were assigned to E transition in tetrahedral environment29. The magnetic susceptibility showed that all Zn(II) complexes (4, 8 and 12) were diamagnetic and the electronic spectra of these complexes do not show any d-d band.The ligands used in this study, coordinate to the metal ions in bidentate or tetrah-edentate fashion, from the azom-ethine nitrogen benzimidazole ring or sulfur atoms or both azomethine nitrogen benzimidazole ring and sulfur atoms in the presence of chloride ion in the coord-ination sphere or outside the coordination sphere as shown in scheme-2. Conclusion By choosing proper experimental condition, the present investigation was made to synthesized 1,2;1,3 and 1,4–bis (benzimidazole-2-thio)ethane or propane or butane and their complexes with Co(II),Ni(II),Cu(II) and Zn(II). From the result , discussion and analysis data it is conformed 1:1 stoichiometry and the electronic spectral data suggest that the Ni(II) complexes have square planer geometry where as Co(II) ,Cu(II) and Zn(II) complexes have tetrahedral geometry. AcknowledgementThe authors are thankful to the chemistry Department. Mosul University and for providing laboratory facilities and the University of AL-Al bait for C.H.N.S. Analysis and HNMR study. Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 43-49, June (2012) Res.J.Chem.SciInternational Science Congress Association 46 NHN S NNH S CHCH M ClCl NHN S NNH S CHCH M ClClCH NHN S NNH S CHCHClCH CH complexe (2)complexes(5,6)complexes (9-12) NH S NH S M ClCl CH_______CH complexes (1,3,4,7 and 8) M = Co(II),Ni(II),Cu(II) and Zn(II) (Schem-2) Table-2 Physical properties of complexes complex no. structure color m.p Analysis found (calc.) %Molar conductivity .cm.mol-1eff C H N S M Cl 1 [Co(L)Cl] Blue 210 43.77 (42.08) 3.08 (3.06) 13.17 (12.27) 14.90 (14.05) 12.59 (12.91) 15.08 (15.54) 21 4.38 2 [Ni(L)Cl] Light brown20942.45 (41.85) 3.67 (3.07) 13.21 (12.28) 14.98 (14.06) 11.42 (12.87) 15.11 (15.54) 34 Di 3 [Cu(L)Cl] Light brown15942.02 (41.66) 3.67 (3.03) 13.09 (12.15) 14.84 (13.91) 13.44 (13.78) 14.59 (15.38) 23 2.22 4 [Zn(L)Cl] White 252-254 42.00 (41.49) 3.54 (3.02) 13.43 (12.10) 14.31 (13.85) 13.77 (14.13) 14.15 (15.32) 30 Di 5 [Co(L)Cl] Blue173 d 44.24 (43.37) 3.99 (3.40) 12.83 (11.90) 14.34 (13.63) 11.63 (12.53) 14.90 (15.07) 39 4.79 6 [Ni(L)Cl] Brown212 d 44.12 (43.40) 3.87 (3.40) 12.01 (11.91) 14.65 (13.64) 11.31 (12.48) 14.97 (15.08) 35 Di 7 [Cu(L)]ClLight yellow250 d 43.55 (42.95) 4.10 (3.36) 12.46 (11.79) 14.04 (13.50) 12.88 (13.38) 14.10 (14.93) 26 1.53 8 [Zn(L)]ClWhite 248-250 44.13 (43.33) 3.71 (3.39) 12.41 (11.89) 14.70 (13.62) 12.96 (13.71)14.58 (14.87) 37 Di 9 [Co(L)]ClDark blue273 d 44.98 (44.60) 3.89 (3.71) 12.11 (11.56) 14.12 (13.24) 11.25 (12.16) 14.40 (14.64) 150 5.08 10 [Ni(L)]Cl Light brown218 d 44.71 (44.62) 3.91 (3.71) 12.09 (11.56) 14.43 (13.24) 11.37 (12.12) 14.62 (14.64) 129 Di 11 [Cu(L)]ClRusty 14344.98 (44.18) 3.89 (3.68) 12.23 (11.45) 14.55 (13.11) 12.58 (12.99) 14.86 (14.50) 163 2.07 12 [Zn(L)]Cl White 210-212 44.70 (44.01) 3.88 (3.66) 12.09 (11.41) 14.12 (13.06) 12.82 (13.32) 14.77 (14.44) 133 Di d=decomposition Research Journal of Chemical Sciences ______ Vol. 2(6), 43-49, June (2012) International Science Congress Association electronic and infrared spectral data of complexes complex no. Band maxima max ) nm 1 314,610,666 1637 2 318,624,664 1651 3 320,472,636 4 332,684 5 322,610,670 6 306,624,692 7 318,340 8 322,574,608 9 308,610,668 10 302,618,692 11 334,434 12 302,572,600 S= strong, m=medium, w= weak ______ _________________________________ ______________ International Science Congress Association Table-3 electronic and infrared spectral data of complexes (C=N) (C-S) (M-N)  1637 S ,1589 m 762 S ---- 1651 S ,1577 m 744 m 482 m 1637 S 731 m --- 1637 S 755 S --- 1637 S 746 S 480 m 1637 S 744 S 492 m 1655 S 735 S --- 1655 S 758 m --- 1577 m 762 S 488 m 1570 S 756 S 492 S 1565732484 1572 S 732 S 499 m Figure-1 Figure-2 ______________ _____ ISSN 2231-606X Res.J.Chem.Sci 47 (M -S) (M-Cl) 360 m 310 w --- 325 w 380 m 312 w 370 m 320 w --- 300 w --- 330 w 360 w 325 w 380 m 315 w 370 m --- 375 m --- 380 w --- 370 m --- Research Journal of Chemical Sciences ______ Vol. 2(6), 43-49, June (2012) International Science Congress Association References 1. Hyappa P.B., Young J.K., Moore J.S. and Suslic K.S. Dendrimer- Metalloporphyrins:Synthesis and Catalysis J.Am. Chem. Soc., 118, 5708 (1996) 2.Castillo-Blum S.E. and Barba- Behrens N., chemistry of some biologically active ligands, Chem. Rev., (3), 196 (2000) 3.Mohan G., and Rajesh N., Synthesis and anti activity of N-Pyridinobenzamide-2- carboxylic acid and its metal chelates, Indian J.Pharm, 24 , 207 4. Kong D., Reibenspies J., Mao J. and Clearfield A., 30-membered octaazama- crocyclic ligand: synthesis, characterization, thermodynamic stabilities and cleavage activity of homodinuclear copper and nickel complexesInorg. Chim. Acta, 342 , 158 5. Pawar N.S., Dalal D.S., Shimpi S.R. and Mahulikar P.P., Studies of microbial activity of N- alkyl and N thiazolyl)-1H-benzimidazoles, Eur. J.Pharm. Sci. (2004) 6. Özden S., Atabey D., Yildiz S. and H.Göker, and Potent Antimicrobial activity of Some Novel or Ethyl 1H-Benzimidazole-5- carboxylates derivatives carrying amide or amidine, Bioorg.M ed. Chem (2005) 7. Ören I., Temiz Ö., , Yalcin I., Sener E. and Altanlar N., Synthesis and antimicrobial activity of some novel 2,5 and/or 6-substituted benzoxazole and benzimidazole derivativesEur. J.Pharm. Sci., , 153 (1998)  ______ _________________________________ ______________ International Science Congress Association Wave numbers/ (cm-1) Figure-3 Infrared spectra of [Co(L)]Cl2 Hyappa P.B., Young J.K., Moore J.S. and Suslic K.S. Metalloporphyrins:Synthesis and Catalysis , Behrens N., Coordination chemistry of some biologically active ligands, Coord. Synthesis and anti -inflammatory carboxylic acid and its , 207 (1992) Kong D., Reibenspies J., Mao J. and Clearfield A., Novel crocyclic ligand: synthesis, characterization, thermodynamic stabilities and DNA cleavage activity of homodinuclear copper and nickel , 158 (2003) Pawar N.S., Dalal D.S., Shimpi S.R. and Mahulikar P.P., alkyl and N -acyl-2-(4- J.Pharm. Sci. , 21, 115 Özden S., Atabey D., Yildiz S. and H.Göker, Synthesis and Potent Antimicrobial activity of Some Novel Methyl carboxylates derivatives ed. Chem ., 13, 1587 Ören I., Temiz Ö., , Yalcin I., Sener E. and Altanlar N., activity of some novel 2,5 - and benzimidazole (1998) 8. He Y., Ww B., Yang J., Robinson D., Risen L., Ranken R., Blyn L., Sheng S.and Swayze E.E., biological evaluations of novel benzimidazoles as potential antibacterial agents, Bioorg.Med.Chem.Lett. (2003) 9.Ayhan- Kilcigil G. and Altanlar N., antifungal properties of some benzimidazole derivatives, Turk.J.Chem., 30, 223 (2006) 10.Yoe- Reyes F.J., Bernes S. and Barba Dichlorobis (1 benzimidazole Crystallog. E61, m875 (2005)11. Sahin E., Ide S., Kurt M. and Yurdakul S., investigation of dibromo bis (benzimidazole) Zn(II) complexJ.Mol. Struc., 616 , 259 12. Sahin E., Ide S.,M.Kurt and Yurdakul S., Structural investigation of dichlorobis (benzimidazole) complex, Z.Kristallogr, 218 ,385 13. Tellez F.H., Sandoral L., Castillo Behrens N.,Coordination behavior of benzimidazole,2 subs tituted benzimidazoles and benzothiazoles, towards transition metal ions, ARKIVOC 14. Gervy J.M., Tellez F., Bernes S., Nöth H., Contreras R. and Barba-Behrens N., Sy nthesis and characterization of new cis-[PtCl (isopropylamine)(amine)] compounds: cytotoxic activity and reactions with 5 with their trans- platinum isomers 532 (2002)         ______________ _____ ISSN 2231-606X Res.J.Chem.Sci 48 He Y., Ww B., Yang J., Robinson D., Risen L., Ranken R., Blyn L., Sheng S.and Swayze E.E., Synthesis and biological evaluations of novel benzimidazoles as potential Bioorg.Med.Chem.Lett. 13, 3253 Kilcigil G. and Altanlar N., Synthesis and antifungal properties of some benzimidazole derivatives, Reyes F.J., Bernes S. and Barba - Behrens N., benzimidazole ) cobalt(II), Acta Sahin E., Ide S., Kurt M. and Yurdakul S., Structural investigation of dibromo bis (benzimidazole) Zn(II) , 259 (2002) Sahin E., Ide S.,M.Kurt and Yurdakul S., Structural investigation of dichlorobis (benzimidazole) Zn(II) ,385 (2003) Tellez F.H., Sandoral L., Castillo -Blum S.E. and Barba- Behrens N.,Coordination behavior of benzimidazole,2 - tituted benzimidazoles and benzothiazoles, towards ARKIVOC , 245 (2008) Gervy J.M., Tellez F., Bernes S., Nöth H., Contreras R. nthesis and characterization of (isopropylamine)(amine)] compounds: cytotoxic activity and reactions with 5 -GMP compared platinum isomers Inorg. Chim. Acta, 339, Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 43-49, June (2012) Res.J.Chem.SciInternational Science Congress Association 49 15.Tellez F., Barba-Behrens N., Flores-Parra A. and Contreras R., Coordination behavior of benzimidazole, 2-substituted benzimidazoles and benzothiazoles, towards transition metal ions, Polyhedron, 22, 2481 (2004) 16.Matthews C.J., Clegg W., Heath S.L., Martin N.C., Stuart M.N. and Lockhart J. C., Coordination of Zn(II),Cd(II)andAg(I) by Bis (benzimidazole) Ligands, Hg(II) Inorg. Chem., 37(2),199 (1998) 17.Buttrus N.H., AL-Smaan S.H. and AL-Asalli S.M., Mono-di-and trinuclear complexes of Co(II),Ni(II),Cu(II) and Zn(II) with 1,4-bis(sodiumthioglycolate) butane, Internation. J. Chem., 20(1), 37 (2010) 18.Abdalrazaq E.A., Buttrus N.H. and Abd AL-Rahman A.A. M.,Synthesis and characterization of gold (III) complexes with bis-(1,4-sodium thioglycolate) butane ligand, Asian J.Chem., 22(3), 2179 (2010) 19.Abdalrazaq E.A., Buttrus N.H., AL-Kattan W.T., Jbarah A.A. and AL-Matarneh M., Reaction of Pd+2 and Pt+2 with pyrrolidinedithio carbamate and cysteine ligands: Synthesis and DFT calculations, J. Sulfur, Chem., 32(2),159 (2011) 20.Vogel A.I., A text Book of Quantitative Inorganic Analysis Including Elementary Instrumental Analysis, ,461 (1967) 21.Geary W.J., The use of conductivity measurements in organic solvents for characterization of coordination compounds, Coord.Chem.Rev. , 8 (1971) 22.Kulkarni P.A., Habib I.S., Saraf V.D. and Deshpande M.M., Synthesis, spectral analysis and antimicrobial activity of some new transition metal complexes derived from 2, 4-dihydroxy acetophenons, Res. J. Pharm. Biol. Chem. Sci., 3, 107 (2012) 23.Buttrus N.H.Synthesis of new disultam niobium(V) and disultam Zinc (II) complexes using disultam mercury compounds, Asian J.Phys.,, 104 (1997)24.Mostafa M.,Metal Chelates of Hydrazone Ligand Chelating Tendencies of 2-Carboxy-phenylhydrazoacetoacetanilide (2-Cphaaa) Ligand, Res.J. Chem.Sci., 1(7),1-4 (2011)25.Manav N., K.Mishra A. and Kaushik N.K., Triphenyl phosphine adducts of platinum (IV) and palladium(II) dithiocarbamates complexes: a spectral and in vitro study, Spectro. Chim.Acta Part A, 60, 3087(2004)26.Chaudhary R. and Shelly, Synthesis, Spectral and Pharmacological Study of Cu(II), Ni(II) and Co(II) Coordination Complexes. Res.J. Chem.Sci., 1(5),1-5(2011)27.Neelama M., Rao P.V. and E-Anuradha G.H.Synthesis and structural studies on transition metal complexes derived from 4-hydroxy-4-methyl-2-pentanone-1H- benimidazole-2yl-hydrazone, J.Chem., 8(1), 29 (2011)28. Hussein S.S.,Mostafa M.,Stefan S.L. and Abdel-Aziz E., Structural Diversity of 3d Complexes of an Isatinic Quinolyl Hydrazon Res.J. Chem.Sci. 1(5),67-72 (2011)29.Buttrus N.H. and Mohammed S.I., Structural diversity of 3d complexes of an istinic quinolyl hydrazone, Mu'tah Lil-Buhuth Wad-Driasat (Jordon), 19(3), 7(2004)