Aggarwal, R. C.

Yadav, R. B. S.

English

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INDIAN J. CHEM., VOL. 15A, JANUARY 1977TABLE 1- ELEMENTALANALYSES*,COLOURAND MAGNETICMOMENTSOF VANADIUM-DITHIOCARBAMATECOMPLEXESomplex ColourFound (%) Calc. (%)[.Left(BM) atCHNSC301°KGrey-green45-827·086·222 045·47,575,906 95·68do37·525 297 8327 133 2Grey31·034 335 1'6917- 9r enishbrown72 589102- 489 ·Light green0'22 -6670 6 4- 'Gre n3 213- 9*'By Dr Alfred BernhardtsMicroanalytical Laboratory, Germany.(a d system) in these ch.elates. These ILeff valuesare omparablewith the value of 1'73BM observedfor is(acetylacetonato)oxovanadium(IV), or otherV(I ) complexes.It is very difficult to assignthe dectror.ic spectralban s in the present complexes, s;nce in suchsyst ms neither of the energyscheme~d Ballhausenand Gray9 or Vanquickenborne and McGlynn10islike to be applicable as such. Besides, muchcont overs}'is prevailing in assigningthe electrodespec ral bands observedfor analogousdithiocarba-mat -oxovanadium(IV) che1ates4,5.T e electronic spectra of [Cp2VL][Ph4B] com-pIe es are approximately similaI*. Two overlap-pin bandsare observedfor thesecomplexesaround16, 0 and 19,000 em-I. Spectra are similar totho e of the corresponding xanthato- and dithio-car amate-complexes3.The bands are not wellres ved and interpretations are difficult. Sym-me ry of thesecomplexesmay be C2V or lower, andin s ch a casenone of the five vanadium d orbitalsre~ins degenerate,and thus the po.."ibility of fourele~ronic transitions exists.e infrared spectra (nujol mull) of all theseco plex s show bands for vV=O, vC:.::.:N, andvC ... S at 985, 1500and 615 em-I (±5-10 em-I)res edively. The band assignmentsare tentativean have been made OD the basis of previouslypu ished work on dith;ocarbamate metal com-pIe es3-5. The observed vV=0 is slightly lowertha the vV=0 observed in VO(acac)2' Thus, itis lear that an incIeased sulphur-to-vanadiumme al 7t-bondingis present in the present L2VOco plexes.ne of the authors (R .K.M.) is thankful to theCS~R' New Delhi, fot the award of a junior researchfell wsbip. They are also th.ankful to Dr S. N.Po dar'of Indian Association for the Cultivatior, ofSci nee, Calcutta, for mull spectra.1. tDEY, K & PODDAR,S. N., Z. anorg.allg. Chem.,327(1964),104; DEY, K, RAY, M. M., PODDAR,S. N.,SARKAR,S. C. N. & HALDER, J., J. Indian chem.Soc.,47 (1970),743; DEY, K & CHATTERJEE, K K, Z.anorg.allg. Chem.,383 (1971),199;DEY, K, CHATTER-JEE, K K & SEN,S. K, J. Indian chem.Soc.,50 (1973),167; DEY, K, SEN, S. K & MAITI, R. K, J. Coord.Chem. (communicated);DEY, K & MAITI, R. K, Z.Naturforsch.(communicated).*:petailedspectraldata can be had from the authors onrequest.so2. DEY, K & MAITI, R K, Z. anorg.allg.Chem.(communi-cated).3. CASEY, A. T. & THACKERAY,J. R, Aust. J. Chem.,25(1972),2085;CASEY,A. T. & THACKERAY,J. R, Aust.J. Chem.,27 (1974),757.4. MCCORMICK,B. J., Inorg. Chem.,7 (1968),1965.5. VIGEE,G.& SELBIN,J.,J. inorg.nucl.Chem.,31(1969),3187.6. KLOPPING,H. L. & VANDERKERK,G. J. M., Reel.Trav.chim.Pays-Bas.Belg.,70 (1951) 936;WELCHER,F. J.,Organic analytical reagents,Vol. IV (Van Nostrand,New York), 1948,82.7. SKACHILOVA,S. YA, SAVITSKII,A. & VLASKINA,R. YA.,Zh. obsch.Khim., 36 (1966),1059.8. GEARY, W. J., Coord.chem.Rev., 7 (1971),81.9. BALLAUSEN,c.J. &GRAY,H. B.,Inorg. Chem.,1(1962),111.10. VANQUICEKNBORNE,L. G. & MCGLYNN, S. P., Theor.chim.Acta, 9 (1968),390.Synthesis& StructuralStudiesof1-Isonicotinyl-4-phenyl-3-thiosemicarbazideComplexesof VO(IV), Co(II), Ni(II) & Cu(I1)R. C. AGGARWAL& R. B. S. YADAVDepartmentof Chemistry,Banaras Hindu UniversityVaranasi 221005Received10 November1975;accepted24 May 1976Complexes of l-isonicotinyl-4-phenyl-3-thiosemicar-bazide (IPTSC) with VO(IV), Co(I1), Ni(I1) and Cu(I1)having the compositions VOS04.IPTSC, CoCI2.IPTSC,Ni(IPTSC-H)CI, Cu(IPTSC-H)Cl and M(IPTSC-2H)[M= VO(IV), Co(I1), Ni(I1) or,cu(I1)] havebeenprepared.The complexes are non-electrolytes in nitrobenzene.The magnetic susceptibility and the electronic spectralstudies have been used to decide the geometry of thecomplexes. The subnormal magnetic moments insome of the complexes have beenexplained by assumingthe presence of magnetically non-equivalent sites inthe unit cell and/or metal-metal interaction. IR spec-tral studies have been used to infer the bonding sitesin the complexes.TRANSITION metal complexes of thiosemi-carbazide, thiocarbazide (an N-aminoderi-vative of thiosemicarbazide) and substituted thio-carbazide have generated considerable interest asrevealedby a recentreview on this subject by AkbarAli and Livingstone1. We thought it fit to prepareand characterizethe nature of 3d metal ion [VO(IV),Co(II), Ni(II) and Cu(II)] complexes with l-iso-nicotinyl-4-phenyl-3-thiosemicarbazide (IPTSC).All the metal salts used were of BDH quality.IPTSC was preparedas describedin the literature2,m.p. 211° (lit.2 m.p. 213°).I II ~NOTESTABLE 1- ANALYTICALDATA,MAGNETICMOMENTSAND SITE SYMMETRYOF 1-ISONICOTINYL-4-PHENYL-3-THIOSEMICARBAZIDECOMPLEXESComplex Colourm.p.MagneticSymmetryFound (%) (Calc.)°CmomenMNSVOS04·IPTSCBr wn3501-51C2v 2-614·750(13'2)( 4-6)'8VO(IPTSC-2H)do245·234'97-005 16(9'5CoCl•.IPTSC*504' 7Td 5043 8-6(14-8)08 )(IPTSC-2H)G eeO';+Td8-457-9)7·Ni(IPTSC- H)Cl*Oa ge4Oh+D h8(16'1)5 32 )Dirty yellow5h D h7·724u279D h IN987 2386 86' 09 0*SatisfactoryCl analyseshave also beenobtained.TABLE 2- ELECTRONICSPECTRALBANDS,THEIR ASSIGNMENTSAND LIGAND FIELD PARAMETERS1IComplexIPTSCVOS04·IPTSCVO(IPTSC-2H)CoCl•.IPTSCCo(IPTSC-2H)Ni(IPTSC-H)ClNi(IPTSC-2H)Cu(IPTSC-H)ClCu(IPTSC-2H)Bands (kK), their assignmentsand values of someligand field parameters30,3 and 37'8L*12·9dxy-+dyz; 14·8dxy-+dxz; 25·0 dxy-+dx'-y'; 30'8 and 40'OL; 36·4 c.t.; Dq =1482cm-I12'9 dxy-+dyz; 15'4 dxy-+dxz; 25·0 dxy-+dx'-y'; 30,8 and 38'5L; 36·4 c.t.; Dq =1539cm-I4·76 4A.-+q. (v,); 7·81 4A.-+q, (F) (v.);16'004A2-+q, (P) (v,);30'3L;25'0 and 36'4C.t.; Dq =476 em-I, B =640 em-I. ~o =26'6%, LFSE =16'3kcaljmole4·88 4A.-+q. (v,); 8·16 4A.-+qIg (F) (V2);16·4 4A.-+q, (P) (v,); 10·02qIg-+4T2g (VI); 26'7and 36·4 c.t. Dq =488 em-I, B =660 em-I, ~o =24'7%. LFSE =16·7kcaljmole14·81 'A2g-+'TIg (F) (v.); 23·53 'A2g-+'TIg (P) (v,); 35'71L; Dq =1018 em-I, B =530 em-I,~o =50%, LFSE =32·0 kcaljmole14'92 'A2g-+'TIg (F) (v.); 23·93'A2g-+'TIg (P) (v,);30,77and 35'71L; Dq =1015cm-', B =525cm-', ~o =50'0%, LFSE =31'9 kcaljmole22·22envelopof 'BIg-+'AIg, 'B2g,'Eg, 26'67 c.t.; 33,33and 41'67L; Dq =2200cm-I15·87envelopof 'BIg-+'AIg, 2B2g.'Eg; 25·33 c.t.; 35,70and 41'67L; D-q =1590cm-I*L stands for ligand and c.t. for chargetransfer transition.Preparatio-n of the complexes-(i) VOS04.IPTSC,CoCI2.IPTSC,Ni(IPTSC-H)CI and Cu(IPTSC-H)CIwerepreparedby mixing ",50 ml of ethanolicormethanolicsolutionsof the metalsalts(15mmoles)and IPTSC (10mmoles).(ii) M(IPTSC-2H) [where M=VO(IV), Co(II),Ni(II) or Cu(II)] werepreparedby raisingthepH ofthereactionmixtureusingsodiumacetateasin (i).The complexesthus precipitatedin each caseweredigestedon a water-bathfor 1 hr, filtered,washedwithwater/ethanolanddriedat 60°.The analyticaldata,magneticmoments3andthesymmetryof the complexesare givenin Table 1.The complexesare insolublein CHCla, CCl4 andpetroleumetherandslightlysolublein nitrobenzeneand solublein polar solventslike ethylenediamineandpyridine. All thecomplexesarenonelectrolytesasisevidentfromtheirmolarconductance« 1·6cm2mho/mole)in nitrobenzene.ThemagneticmomentsofCoCl2.IPTSC,Cu(IPTSC-H)CI andCu(IPTSC-2H)arenormalandlie well inthe rangesreported4for tetrahedralcomplexesofCo(II) andsquareplanarcomplexesof Cu(II). Thesubnormalmagneticmomentsof VO(IV) complexesareattributedto VO- - -V interactionwhilethoseofNi(II) complexesareconsideredto be dueto theirpolymericstructuresconsistingof both planarandoctahedralNi(II) atoms in the unit ce115•Themagneticmoment4·01 BM of Co(IPTSC-2H) isslightly belowthe lower limit of the tetrahedralcomplexesof Co(II) , suggestinga tetrahedralstruc-'turewithsomemetal-metalinteraction.Electronicspectralstudies- Theelectronicspectra(nujol,Cary14)ofall thecomplexesexhibitedbandsat 30·7-35·7and36·4-41·7kK regionswhichcorres-pondto 28·57and40·00kK bandsof IPTSC andhencemay be assignedto intraligandtransition·(Table2)..Therehasbeena lot of controversyregardingtheenergylevel sequenceof the d-orbitalsin VO(IV)ion in C2v symmetry6-s.In the presentlypreparedVO(IV) complexeswith IPTSC, the bandsat 12'9,14·8-15·4and 25 kK have beenassignedto thetransitionsdxy-+dyz,dxzanddx2_y2 respectivelyinconformitywithWassonetal.s.The bandsat 4·76,7·80and 16·00kK in CoCIl!'IPTSC arecharacteristicoftetrahedrallycoordinatedCo(II). The splittingof thesebandsgivesfurtherindicationof tetrahedralcoordination8in theabovecomplex. In additionto thesebandsthe spectnlmofCo(IPTSC-2H)showsbandsat 10·00and16·40kKcharacteristicof octahedralcoordination.This in-'dicatesa certainamountof metal-metalinteractionarisingfrom dimericor polymericstructureof thecomplex. Thisissupportedbythemagneticmomentvalueof 4·01BM for this complex.51R C. PAUL,B. N. ANAND& R KAPOORDepartmentof Chemistry,PanjabUniversityChandigarh160014Received3 March 1976;accepted3 June 1976Synthesisof SubstitutedDimethylformamidylTe(IV) & Se(IV) ChloridesIN continuation of our earlier report! on thepreparationof alkali metal dimethylformamidyls,we now report the preparation and characterizationof substituteddirnethylformamidylcompounds,TeC13-CON(CH3h·DMF ard SeC13CON(CH3)2of Te(IV)and Se(IV) chlorides.Preparation of TeCt3CON(CH3)2.DMF (I) - Onstirring an equimolar mixture of TeC14and NaCON(CH3)2in CC14for 7-8 hr, a dark brown volumiJ1.oussolid separated which ',\0as filtered, washed withSubstitutedimethylformamidyltellurium(IV)chlo-ride[TeCI3CON(CH3)••DMF]andselenium(IV)chloride,SeCI3[CON(CH3).] havebeenpreparedby thereactionof TeC14andSeCl4with dimethylformamidylsodium.The compoundshavebeencharacterizedon thebasisof elementalanalyses,molar conductanceand IRspectraldata.(R=isonicotinyl)i INDIAN J. CHEM., VOL. 15A,JANUARY 1977Mi$d stereochemistry (Oh+D4h) was proposed Oneof the authors (RB.S.Y.) is thankhl tc (SIR,for ]'(II) complexes on the basis of magnetic New Delhi, fer financial assistance.marne t data. The electronic spectra of these R Ge.erencescamp xes show bands at about 10·00, 14·8 and23'5 K characteristic of an octahedral gecmetry. 1. AKBARALl, M. & LIVINGSTONE,S. E., Coord. Chem.Th k .. b d h t" f N'(II) . Rev 13 (1974)10e ea mtensIty. an c arac ensilc 0 I III 2. KOR~~I,J., Egy~suliGyogyszeres Tapszergyar(Hung.),squar planar envIronment appears to have sub- 148(1962),949.merg in thestrongintensity '.12 bandof cctahedrally 3. FIGGIS,B. N. & LEWIS,J., citedin Moderncoordinationcoord nated Ni(II). chemistry,/ditedby J. Lewis& R G. Wilkins(Inter-Th 22·22 and 15·87kK bands in the spectra of SCIence,NewYork), 1962.C (IP SC H)Cl d C (IPTSC 2H) . d' t 4. KENT,BAREFIELD,E. BUSCH,D. H. & NELSON,S. M.,u -. an . u - III Ica e squ~re Q. Revs.,22 (1968),457.plana and hIghly dIstorted octahedral geometnes 5. KANEKAR,C. R & CASEY,A. T., ]. inorg.nucl. Chern.,respe4tivelyfor the two complexes. 31 (1969),3105.! 6. DRAKE,J. E., VEBRIS,J. & WOOD,J. S., ]. chem.Soc.,I R _ NH _ NH _ CS_ NHPh (A), (1968),1000.I 7. KUSKA,H. A. & YANG,P. H., Abstractof the5thCentralRegional Meeting of the American ChemicalSociety,Cleveland,Ohio, 13-15May 1973.8. STOKLOSA,H. J., WASSON,J. R & CORMIC,J. Me.,Inorg.Chem.,13 (1974),592.9. SINGH,P. P. & RIVEST,R, Can. ]. Chem.,46 (1968),2361.10.NAGANO,K., KINOSHITA,H. & HIRAKAWA,A., Chem.Pharm. Bull., 12 (1964),1198;1207.11.DUTT,N. K. & CHAKDER,N. C., J. inorg. nucl. Chem.,32 (1970),2303.12.BRAIBANTI,A., DALLVALLE,F., PELLINGHELL,M. A. &LAPARATI,E., Inorg. Chem.,7 (1968),1430.13.CORMIC,B. J. Mc.,BOZIS,R A., Inorg. Chem.,10(1971),2806.14.MATHEW,M., CARTY,A. J. & PALENIK,G. J., J. Am.chem.Soc., 92 (1970),3197.15.ESKENAZI,R, ROSKOWAN,J. & LEWITUR,R, ]. inorg.nucl. Chem.,28 (1966),521.16.SPECA,A. N., KARAYANIS,N. M. & PYTLEWSKI,L. L.,Inorg. chem.Acta, 9 (1974),87;]. inorg. nucl. Chem.,36 (1974),3751.17.TEOTIA,M. P., RASTOGI,D. K. & MALIK,W. R, Inorg.chim. Acta, 7 (1973),339.18.BEECROFT,B., CAMPBELL,M. J. M. & GREZESKOWIAK,R, J. inorg. nucl. Chem.,36 (1974),55.19.BROWALL,K. W. & INTERRANTE,L. V.,]. Coord.Chem.,3 (1973),27.20.MASSACEST,M. & PONTICELLI,G., ]. inorg.nucl. Chem.,36 (1974),2209.A ~egative shift in v(N-H) bands in all thecomptexesexcept in the caseof VO(IPTSC-2H), ascomp redwith the solution spectrum(in acetonitrile)of th ligand indicates the involvement of at leastone 0 th )N -H groups in b nding. The amide-Iband! suffers a negative shift in the spectraof th~ adducts as ccmpared with the free ligandand disappears in the spectra of condensaticncomp£unds, indicating the involvement of the)C=? group of he ligand in coordinaticn inthe a~ductsand the destructicn of this grcup pre-SUma ly via enolization in the latter ccmplexes.A ositive shift of about 30 cm-1 in the ringvibr ion in the spectraof the adductsand of about60 ct-1in those of condensation c(jmpounds ascomp red with the solution spectrum of the parentligan suggeststhe involvement in coordination ofthe c~rb()nyloxygen in the adducts and carbcnyloxyg$ as we l aspyridine nitrogen in the latter10.Th~ v(C=S+C-N) modell is either very weakor difappears completely in the spectra of con-densa ion products M(IPTSC-2H) [M=VO(IV),Co(II , N.i(II) and Cu(II)] but shifts to the higherfrequ ncy side in the sp ctra of t e adducts such asVOS~4.IPTSC' CoC12.IPTSC, Ni(IPTSC-H)Cl andCu(I' TSC-H)Cl indicating the destruction of thethiok to group in the former complexes and non-parti ipation of the )C=S group in the lattercomp~exes.Th~ positive shift in the v(N-N) mode in thespectta of all the complexesindicates the involve-mentlof one or both of the nitrogens in bondingI2.Th lower value of v(V-=O) in VO-IPTSC Cf m-plexe~ as compared with a number of VO(IV)comp.exes13,I4m y be due to the existence ofV=q- - -V interaction. This is in accord withthe s~normal magneticmomentsof theseccmplexesdiscu sedearlier. The bandsat 1100-1125,1025and975 -1 in the spectrumof VOs04.IPTSC may beattri tited to the chelatingsulphatogroup15.Th l w frequency bands in 435-390and 308-292cm-1~egionsin all the IPTSC complexesare ten-tativ¢ly assigned16•17to v(M-O) and v(M-N)(ref.• 6, 18) modesrespecti ely. The 384-368cm-1regio* band in theunchargedcnmplexesand 342-333cm-1fgion bandin CoCl2.IPTSC and Cu(IPTSC-H)Clmay e attributed to v(M-S) (ref. 19) and v(M-Cl)(ref. I 0) modes respectively.52 II~ I

Synthesis & Structural Studies of 1-Isonicotinyl-4- phenyl-3 -thiosemicarbazide Complexes of VO(IV), Co(II), Ni(II) & Cu(II)

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Synthesis & Structural Studies of 1-Isonicotinyl-4- phenyl-3 -thiosemicarbazide Complexes of VO(IV), Co(II), Ni(II) & Cu(II)

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