Lal, R. A.

Narang, K. K.

English

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INDIAN J. CHEM., VOL. 14A, JUNE 1976TABLE 2 - COLOURANDANALYTICALDATAOF Ni(II)COMPLEXESCompound Colour N (%) Ni (%) M (%)Calc. Calc. Calc.(Found) (Found) (Found)Ni(H. DAPL) Yellow 6·56 12'87Ni(Li.DAPL).4H.O(6,48) (12'02)do 5-48 11·48 2-71Ni(Na.DAPL).4HIO(5'39) (11'26) (2'81)Orange 5·16 11'18 8·46Ni(Mg DAPL).2H.O(5'37) (11'66) . (8'51)Yellow 5'77 12·10 5·01Ni(Ca DAPL).3H.O(6'48) (12-60) (4'75)do 5'39 11·31 7·72Ni(Sr DAPL).3H.O(HI) (11'26) (7'10)do 4'94 10·35 15·45Ni(Ba DAPL).5H.O(5040) (10'62) (15'06)do 4·45 9·00 21·07Ni(H. DAMPL)(4-89) (8·39) (21'67)do 6'35 26'53Ni(Na. DAMPL).2·5H.O(6'32) (26'80)Red 5'28 11'08 8·67Ni(Li. DM'IPL).3H.O(5'13) (11'72) (8'01)do 5·52 11·58 2·74Ni(Mg DAMPL).6H.O(5-89) (10'71) (2'82)Yellow 4'90 10'28 4·26Ni(Ca Dfu"IPL).5H.O(4060) (9,36) (3'51)Orange 4'92 10·32 7·04Ni(Sr DAMPL).4H.O(4'76) (10'40) (6'93)do 4'67 9·80 14·63Ni(Ba DAMPL).3H.O(4·70) (9'82) (14060)do 4·45 9'32 21'80(4·16) (9'18) (20'98)violet, ~ere obtained. The grey form was preparedby adding BaCl2 (1 g) solution to an excess Cu(Na2DAPL).4H20.Preparation of Ni(Na2DAPL) and Ni(Na2DAMPL) - Schiff base (2 g) dissolved in aqueousNaOH 0·6 g dissolved in 75 ml H20 was heated ona steam-bath and to this Ni(OAc)a(---0·05M in 100ml absolute ethanol) was added slowly with stirring.The solution turned dark-red which on cooling de-posited the orange-red silky needles of the disodiumderivative of Ni(II) complex. The solution wasfiltered, washed with ethanol, and dried in vacuo for24 hr over silica gel.Reaction of Ni(Na2DAPL) and Ni(Na2DAMPL) withI A and I I A group elements - The parent complex(O'LM) was dissolved in water (100 ml) and heatedon a steam-bath. To this was added a solution ofLiCl (0·08M) dil. HCI or a solution (0·04M, 100 ml) ofMgS04, CaCl2, Sr(N03}2' or BaCI2• In most for thecases immediate precipitation occurs. The mixturewas heated on a steam-bath for 30 min, cooled andfiltered. Finally the precipitate was washed anddried in vacuo over silica gel for 2-3 days.The diffuse electronic (reflectance) spectra weremeasured on a Zeiss PMQ II spectrophotometer withthe sample spread on a filter paper. The roomtemperature magnetic susceptibilities were measuredby the Gouy method.The author is grateful to the UGC, New Delhi,for the award of a Colombo Plan Fellowship. Heis also thankful to Dr D. J. Phillips of the Schoolof Chemistry, University of New South Wales, forsuggesting the problem and for helpful suggestions.442References1. HARRIS, C. M. & SINN, L., Coord. cu«. Rev. 4 (1969)391. ' ~2. PODDAR,S. N., Z. anorg. allg, Chem., 322 (1963), 326.3. PHILLIPS, D. J. & CUNNINGHAM,J., unpublished work ..4. DUFF, J. & BILLS, E., J. chem, Soc., (1932), 1987.Zn(II), Cu(II), Ni(II) & Co(II) Complexes ofN-(Salicylidene )-N' -[2-( salicylaldimine)-benzoyl]hydrazine, the Schiff Base Derivedfrom o-Aminobenzoylhydrazine &SalicylaldehydeK. K. NARANG& R. A. LALChemistry Department, Banaras Hindu UniversityVaranasi 5Received 1 July 1975; accepted 16 August 1975Zn(II), Cu(II), Ni(lI) and Co(lI) complexes of N-(saUcylidene)-N' -[(2-saUcylaldimine )benzoyl]hydrazh~e,.the Schiff base derived from o-amlnobenzoylhydraslneand saUcylaldehyde, (LH) have been synthesized andcharacterized on the basis of analytical, electronic andinfrared spectral and magnetic moment data.MONOAMINE oxidase (MAO) enzyme inhibitionby. acylhydrazinest-P has been suggested to takeplac~ via met?-l-acylhydrazine Schiff base complex''.In VIew of this and because of very little work re-ported on the complexes of Schiff bases derived fromhydrazine and acylhydrazines, we report in this notethe prep~ration and characterization. of Cu(II) ,Zn(II) , Nl(II) and Co(II) complexes with the titleligand (I).Th.e ligand (I) w.as prepared by condensingo-aminobenzoylhydrazines and salicylaldehyde in1:2 molar ratio and cystallizing the product fromethanol; m.p., 2180 (Found: C, 71·01; H, 5·00; N,izio Reqd: C, 70·19; H, 4·74; N, 11'70%)Cu(II) and Ni(II) complexes (b, c and d; Table I}were prepared by reactmg Cu(II) and Ni(II} chlo-rides and the ligand in 1: 1 and 1: 2 (metal: ligand}molar ratios in hot ethanol. The products werefiltered and washed with hot ethanol. Complexes.a, e ?-nd f (Tabl.e 1) vyere prepared by reacting asolution of the ligand III NaOH with excess metalsalts and acidifying the resultant mixture withacetic acid. The solids obtained were filtered.washed with dilute acetic acid and hot ethanol and,dried at room temperature.The ligand in the complexes was estimated volu-metrically in toN H2S04 with standard KMnOusing a calibration curve. The complexes wer:o OH1\ 1 2 ~/" \ C-NH-N=CH 0(J(3N=CH~HO~I'I INOTESTABLE 1 - ANALYTICAL, ELECTRONIC SPECTRAL AND MAGNETIC DATA OF Zn(II), Cu(Il), Ni(II) AND Co (II) COMPLEXESComplex and colour rn.n. Found (Calc,), (%) iJ.eff. ),max (nm)(0(;) (ml)Metal N Ligand(a) ZnL. 202 7·9 11·5 91·1 Diamagnetic 235, 250, 300, 370light yellow (8'3) (10,8) (91'6)(b) CuL. 155 7'7 10·7 92'5 1·6 240, 285, 387, 430. 687deep green (8'5) (10'8) (91'9)(c) [CuL]Cl 170 13'9 10·00 80'0 1·8 305, 362, 437. 600green (14-4) (9'30) (79'5)(d) [NiL]Cl 240 13·6 9'7 78'5 3·3 263, 320, 400, 600light green (13'1) (9'3) (79'1)(e) NiL. 240 8·1 11·2 93·0 3'1 235. 260, 315, 438yellow (7-6) 110·8) (92-4)(f) CoL. 230 7·2 11·4 92·9 1'9 250, 375brown (7-6) (l0'8) (92-4)analysed for nitrogen using a Coleman nitrogenanalyser, and for the metal by usual procedures.Infrared and electronic spectra were recordedon a Perkin-Elmer spectrophotometer model621 and a Cary-14 model spectrophotometer res-pectively in nujol. Magnetic measurements werecarried out on a Faraday balance.Cu(II) forms both 1: 1 and 1: 2 (metal-ligand)complexes (Table 1) depending on the metal-ligandratio used but Ni(U) forms only 1: 1 complex evenwhen Ni(II) salt and the ligand are reacted in 1:2molar ratio. The chloride ions are partially replacedin the complexes (c and d Table 1) prepared fromethanolic medium. Under similar conditions. Co(II)complex fails to precipitate. The alkaline solutionof the ligand, however, reacts with Zn(II),Ni(II) and Co (II) salts forming neutral complexes.The comnlexes are coloured, insoluble in water andcommon' organic solvents but dissolve slightly intetrahydrofuran and nitrobenzene unlike the amineschiff base complexes. The ligand loses one protonin both 1: 1 and 1: 2 complexes. It has three labileprotons, viz. those of one '-NH and two -OH groupsout of which the -OH protons are more labile. Since,the -OH groups are hydrogen bonded as in Schiffbases, the one which is strongly hydrogen bondedmay be strongly ionized and hence more labile. The3electrons on N being in conjugation with twobenzene rings (I), are less available for hydrogen2bonding than those of 1'\ which is in resonance withonly one benzene ring. Although both the -OHprotons should be reactive in alkaline medium, the'1: 2 compositions of Zn(II) , Ni(II) and Co(II) com-plexes (a, e and f, Table 1) indicate that. one ?f the-OH group is re-formed when the reaction mixtureis acidified with acetic acid. From these observa-tions and previous experiences:", it can be said that2OR group of salicylidene moiety on N takes partin coordination.The visible spectrum of the ligand shows bandsat 245 and 337 nm. In the metal complexes thesebands are shifted considerably (Table 1). Cu(I!)complexes (b and c) show one band in the redregion (......,600nm) due to the transition 2T2g~2Egcorresponding to planar structure". Octahedral,Ni (II) complexes show two bands correspondingto the transitions 3Au-+3TIg(F) and 3A2g-+3Tu(P)respectively". In the present Ni(II) complexes (dand e) the band corresponding to the transition3A 2g-+3T2g(P) is masked by a charge-transfer bandbut a band around 600 nm is present in complex (d).Infrared spectra (band positions in cm-I) of theligand and its metal complexes show a band around3400 indicating the presence of -OH group. A broadband (',IN-H) centred at 3200 in the ligand is shiftedto 3340 in metal complexes. This increase invN-H frequency is analogous to a similar increasein vN-H in the complexes of secondary amides when> C=O group coordinates", The vC=O bandobserved at 1640 in the ligand shifts to lowerfrequency side (~v = 20) in metal complexes,confirming the involvement of > C=O group incoordination.The Cu(I!) complexes (b and c) show (.teff. valueswhich are slightly less than those expected for oneunpaired electron. As the visible spectral bandin the case of complex (c) is shifted more towardsthe blue region, it indicates the greater planarityof the co~pJex. ~ue to this increased planarity,some M-M interactions may have caused the loweringof magnetic moment.One of the authors (R.A.L.) is thankful to the CSIRNew Delhi, for the award of a junior researchfellowship.References1. ZELLER, E. A .• BARSKY. J.. FOUTS (Jr), KlRCHHEIMER,'.V. F. & VAN-ORDEN, L. S., Experimentia, 8 (1952), 349.2. YONEDA, M., KOTA, X. & OKA]IMA, Nature, 170 (1952).803.3. WEIGAND, R. c.. J. A 1t/. chem, Soc., 78 (1956), 5307.4. PRAGER, B., JACOBSON. P .• SCHIMDT, P. & STERN, D.,Belstein hand bucb der organischen Chemie, 14 (1931). 323.5. NARANG, K. K. & AGGARWAL, A., Indian]. Chem., 13(1975), 1972-6. ::-;-ARANG, K. K. & AGGARWAL, A., Tnorg, chim. Acta, 9(1974). 137.7. SACCONI, L. & CIAMPOLINI. M., J. chem. Soc., (1964). 276.8. BALLHAUSEN. C. J.. Introduction to ligand field theory(McGraw-Hill, New York). 1962, 256.9. PAUL, R. C. & CHADHA, S. L., J. inorg, nucl, cu«, 31(1969), 2753.443

Zn(II), Cu(II), Ni(II) & Co(II) Complexes of N-(Salicylidene)-N'-[2-(salicylaldimine)- benzoyl]hydrazine, the Schiff Base Derived from o-Aminobenzoylhydrazine & Salicylaldehyde

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Zn(II), Cu(II), Ni(II) & Co(II) Complexes of N-(Salicylidene)-N'-[2-(salicylaldimine)- benzoyl]hydrazine, the Schiff Base Derived from o-Aminobenzoylhydrazine & Salicylaldehyde

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