Azaidi, S A

Khan, Tabrez A

Shaheer, S A

Zaidi, S Rehan A

English

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IndianJournalof ChemistryVol.26A, December1987,pp.1056-1058Synthesis&VibrationalSpectraofDioxo-uranium(VI),Th(IV), Zr(IV) & Oxozir-conium(IV)Chlorosulphates&TheirComplexeswithSomeOrganicDonorsS AAZAIDI*,SREHAN AZAID1~SA SHAHEER & TABREZ A KHANDivisionof InorganicChemistry,Departmentof ChemistryAligarhMuslimUniversity,Aligarh202001Received5 Jam-wry1987;revisedandaccepted12March1987Solvolysisof uranyl,thorium,zirconiumandzirconylacetatesinchlorosulphuricacidresultsintheformationofthecompoundsof compositionsU02(SO,Cl)2' Th(SO,CI)4' Zr(SO,CI)4 andZrO(50,CI h,respectively.Thepresenceofstrongmetal-chioro-sulphatecovalentinteractionhasbeeninferredfromtheIR dataofthecompounds.Th(IV) andZr(IV) chlorosulphate:sseemto beeight-coordinatedwhile dioxouranium(VI) and oxozirconi-um(IV) chlorosulphatesare six- andfive-coordinated,respect-ively.Their complexationwithpyridine"pyridineN-oxide,acri-dine,and1,1O-phenanthrolinehasalsobeenstudied.Earlierreports]- 4fromourlaboratorydescribedthesynthesisandcharacterizationof varioustransitionmetalandlanthanoncWorosulphatesandtheircom-plexeswithseveralorganicdonors.Wereporthere,the preparation and characterization ofU02(S03Clh, Th(S03Cl)4, Zr(S03Cl)4 andZrO(S03Clh and theiradductswithsomeorganicdonors.Out of these,U02(S03Clh andTh(S03Cl)4havebeenpreparedearlier5by a slightlydifferentmethodalongwiththeiradductswith2,2'-bipyridyl,triphenylphosphineand triphenylphosphineoxideonly.All thereagentsusedwereof AR grade.Chloro-sulphuricacid(Riedel),metalnitratesandtheligandslallBDH reagents)wereusedassuch.Solventsweredistilledbeforeuse.The anhydrousacetateswerepreparedby reflux-lngthemetalnitratesa mixtureof aceticanhydrideandaceticacid(60:40,vIv) takeninexcess.The reac-tionwashighlyexothermicin natureandhadto be~arefullymonitoredinitially.PreparationofthemetalchlorosulphatesAnhydrousmetalacetates(0.05mol)weretakeninareactionvesselandanexcessofcWorosulphuricac-idwasslowlyadded.Whenthereactionsubsided,thecontentsweremagneticallystirredfor aboutthreehours.The precipitatedcompoundswerefilteredinvacuo,washedseveraltimeswithneatchlorosulphu-ricacidandthionylchlorideandfinallydriedinvacuoJ05hto a constantweight.The solidsthusisolatedwerefoundtobehygroscopicin nature.Preparationof thecomplexesMetalchlorosulphates(0.05mol)inbenzeneweremixedwiththehotligandsolution(0.5mol)indime-thylformamideandtheresultingmixturewasstirredforabout4-5 days.Thecompoundsthusformedwerefiltered in vacuo,washedwith benzene,dimethyl-formamideanddryetherandfinallydried in vacuo.TheestimationsofC,HandN weredonemicroan-alytically.Chlorineandsulphurwereestimatedasre-ported],3.Metalswereestimatedbyknownmethods.Infraredspectrawererunon aPerkinElmer 621spectrophotometerasreportedearlier3.Theelectri-calconductivitiesweremeasuredonaSystronic302conductivitybridgethermostatedat ±0.05°C.Ex-perimentswereperformedinagloveboxflushedwithdryN2·Uranyl, thorium,zirconiumandzirconylchloro-sulphateshavebeensynthesizedbycarryingoutthesolvolyticreactionsof thecorrespondinganhydrousmetalacetateswithchlorosulphuricacidaccordingtothefollowingreaction:M(CH3COO)n+nHS03Cl--+M(S03Cl\, +nCH3COOHM =Zr, Th, n=4;UOc,ZrO,n=2.TheanalyticaldatalistedinTable1areconsistentwiththeproposedformulations.Theinfraredspectraof thesechlorosulphatesdisplaytheninefundamen-tal modesof vibrationcharacteristicof a bondedchlorosulphategroupl.2. Thepositionofthesym.S03stretchingvibrationvj(A) (1070-1080cm-I) andthemagnitudeofthesplittingoftheEmodesofvibra-tion(asaconsequenceof thesymmetrylowering;'inthesechlorosulphatesindicatetheexistenceofasub-stantialcovalentinteractionbetweenthemetaland(S03Cl)- group.The valuesof vsS03 bandsareingoodagreementwiththosereportedfor thebridgingbidentateS03Cl groups.The splittingof thev6(£)modeisnotobserved,butarelativelyweakbandhasbeenfound in the region290-320cm- I. The re-semblanceof thelR spectraof thesechlorosulphateswith thoseof the correspondingf1uorosulphates6,whereblidgingbidentatenatureof the f1uorosul-phatesgrouphasbeenproposed,providesa goodevidenceforthebidentatecoordinationofthechiom-sulphategroup.ThecharacteristicVu ~0 andVZr ~0 bands7areob-servedin U02(S03Cl)zandZrO(S03Cl)zat - 960'11'11 '1,11 I I INOTESTableI-AnalyticalDataoftheComplexesCompoundFound(Calc.),%CHNMSClU02(S03Clh--, -46.5911.915.0(47.41)( 2.75)14 3U02(Pyh(S03Clh19.31.404.3937. 19 5610 6(18.22)( .53)5.25)(36.119 370 76NOh(S03Clh6 03953 048 889( 6.70)1 403 893 098 929 6U02(Acr ( l35 932 123268. 13 33227 6PhenXS03Clh43.760 5244 6644 4Th(S03Cl)432 717 3933 338 9(Py (S03Cl)4675609825 06 4NOh( )423.1705 6Acrh(S03Cl)40 17367296 517henX )446 5148Zr( l)17.024 916 92Pyh(S03C1)48839 39 4 55 47.3 7(7 9. ) )8O(SOP2 8 882 841 2l25 4 2( l11 5881rh(S03Clh1O ot( 0( . 2222 3Py, PyNO, Acr andPhenrepresentpyridine,pyridineN-Oxide,acridineandphenanthr li e,respectively.cm- ].A bandof mediumintensityat 240cm-] inU02(S03Cl)zmaybe assignedas O-U-O bendingmode.The v] modeof theuranylgroupisIR-forbid-deninthefreelinearionandtheabsenceofabandas-signabletothismodeat - 850cm-] indicatesthatthelinearityof theO-U-O groupismaintained.The lowmolarconductancevaluesof thesechlorosulphates(26-28 cm2mol-1ohm- 1) are consistentwith theirnon-electrolyticnatureandfurthersupporthecova-lentlinkageoftheS03Cl- grouptothecationoroxy-cation.If allthethree(S03Cl)- groupscoordinateinabi-dentatemannerthenthemetalatomwill be eight-coordinatedin Zr(S03CI)4 and Th(S03CI)4'Al-though many hexacoordinatedcomplexes areknown, relativelyfew octa-coordinatedzirconi-um(IV) complexesare reported8•The complexesU02(S03Cl)2andZrO(S03Clhmaybeconsideredtoinvolvesix-coordinateduraniumandfive-coordinat-edzirconiumwithfouroxygenatomsasdonorsfromtwobidentatechlorosulphategroups.The analyticaldatain Table1areconsistentwith1:2(metal:ligand)stoichiometryforallthecomplexesexcepthephenanthrolinecomplexeswheretheme-tal:ligandratiohasbeenfoundtobe 1:1.Theobservedupwardshifts( - 30cm- 1) intheab-sorptionbandsfoundat1595(pyridineringdeforma-tion),620(in-planeringdeform)and430cm- I (out-of-planeringdeform.)in thepyridinecomplexesareconsistentwiththeinvolvementofpyridinenitrogenatomincoordinationtothemetalions9•Thesplitting1057INDIAN J. CHEM., VOL. 26A, DECEMBER 1987of the pyridine bands presumably arises from the in-termolecular or intramolecular interactions betweendifferent pyridine molecules in the crystal lattice 10.The characteristic VN _ 0 vibrations in the pyridine-N-Oxide complexes show significant shifts to lowerwave numbers ( - 25 em - 1) indicating complexationwhich may be attributed to coordination of the oxy-gen atom of the base causing decrease in Jt -characterof the N-O bond 11. The bands observed in 350-400em - 1 region are assigned to vM-O frequency 12.The vc~c and VC~N vibrations occurring at 1515and 1555 em -1, respectively, in the free acridine ap-pear in the complexes at a higher frequency around1540-1550 and 1573··1580 em -I, respectively, indi-cating coordination through the nitrogen atom of theacridine molecule-v'". The bands observed at 415-550 ern - 1 are assigned to vM- N mode. The charac-teristic bands (1505 and 1650 em - 1) ofthe free phen-anthroline undergo appreciable shifts to 1520-1530and 1630-1645 em - \ respectively, on complexa-tionl '.The positions of VSS03 frequencies in these com-plexes (1080-1085 em - I) indicate the bidentate na-tureofthechlorosulphate group. The Vu~ 0 and VZr~Obandsappearatlowerwavenumbers(910-920cm -1)which may be ascribed to the change in U= 0 andZr =0 bond order in view of the increased electrondensity around the metal.The diamagnetic nature of the zirconium com-plexes and absence of any d-dtransition confirm thequadrivalent state of the metal ion.1058We thank CSIR, New Delhi for financial support tothree of us (SRAZ, SAS and TAK). We also thankProf. M.S. Ahmad, Chairman of our Department, forproviding research facilities.References1 Siddiqi Z A, Shakir M, Aslam M, Khan T A & Zaidi S A A,Synth react inorg met-org Chern, 4 (1983) 397.2 SiddiqiZA,AslamM,ShakirM&ZaidiSAA, Synth reactin-org met-org Chem, 11 (1981)475.3 Zaidi S A A, Zaidi S R A, Shakir M, Aslam M & Siddiqi Z A,Polyhedron, 4 (1985) 365.4 Zaidi S A A, Zaidi S R A, Khan T A, Shaheer S A & Siddiqi ZA, Indian J Chern, 25A (1986) 779.5 Singh S, Maninder & Varma R D, Indian J Chern, 23 (1984)1038.6 Edwards D A, StiffMJ & Woolf AA, Inorgnucl chem Lett,3(1967) 427.7 Barraclough C G, Lewis J & Nyholm R S, J chem Soc, (1959)3552; Kraussss H L & Huber W, Ber dt Chern Ges, 94(1964) 856.8 Larsen E M, Advances in inorganic chernistryand radiochem-istry, edited by H J Emeleus & A G Sharpe (AcademicPress, New York), Vol 13. 1970. 1.9 Gill N S, Nuttal R H, Scarfe D E & Sharp D W A, J inorg nuclChern, 18 (1961) 79.10 Clark R J H & Williams C S, Inorg Chern, 4 (1965) 330.11 Srivastava TN, Srivastava P C & Bhatra N,J Indian chern Sac,55 (1978)434.12 Ferraro JR, Low frequency vibrations of inorganic and coordi·nation cornpounds(Plenum Press, New York), 1971.13 Zaidi SA A & Siddiqi K S, J inorg nucl Chern, 35 (1973) 655.14 Zaidi S A A, Siddiqi K S & Neelam N S, Indian J Chern, 14(1976) 209.15 Schilt A A & Taylor R C, J inorg nucl Chern, 9 (1959) 211."II\chMHeCOIpieree4,ltiohlIlategarTba kpreeth(anratirna:metbatlanoconremIn ~plexAsstonCanalwe'rerespwerenujolas dicm-Iwas ITGtdey ~

Synthesis & Vibrational Spectra of Dioxouranium(VI), Th(IV), Zr(IV) & Oxozirconium(IV) Chlorosulphates &Their Complexes with Some Organic Donors

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Synthesis & Vibrational Spectra of Dioxouranium(VI), Th(IV), Zr(IV) & Oxozirconium(IV) Chlorosulphates &Their Complexes with Some Organic Donors

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