【doc】二维层状结构十钒酸盐[K（H2O）2Ni（H2O）6]2[V10O28]的合成及性质

【doc】二维层状结构十钒酸盐[K（H2O）2Ni（H2O）6]2[V10O28]的合成及性质 二维层状结构十钒酸盐[K(H2O)2Ni(H2O) 6]2[V10O28]的合成及性质 第9期 2004年9月 无机化学 CHINESEJOURNALOFINORGANICCHEMISTRY Vo1.20.No.9 Sep.,2004 睇睇嗡 ?5研究简报 二维层状结构十钒酸盐[K(H2O)2Ni(H2o)d2[VoO28]的合成及性质 关键词 分类号 李德慧刘术侠彭军邵奎战许洪彬翟宏菊王恩波 十钒酸盐 O614.113 (东北师范大学化学系多酸研究所,长春130024) 合成二维层状结构×-射线晶体结构 O614.810614.511 SynthesisandCharacterizationof2DLayeredStructure Decavanadate【K(H20)2Ni(H20)612IV10o28】 LIDe—HuiLIUShu—XiaPENGJunSHAOKui—ZhanXUHong—BinZHAIHong—JuWANGEn—Bo (InstituteofPolyoxometalateChemistry,FacuhyofChemistry,NortheastNormdUniversity ,Changchun130024) Anovelheteropolycompound,containingtwokindsofcoordinatedcations,[K(H2O)2Ni(H 2o)612IVloO28],has beensvnthesizedthroughroutineprocessandcharacterizedbyelementalanalyses,IR,VNMRandsingle crystalX— ravdiffraction.Itcrystallizesinthetriclinicsystem,spacegroupP1witha=0.87382(17)nm,b=1.0754(2) nm,c=1.1111f2)nm,a=65.10(3).,/3=75.O1(3).,y=70.63(3).,V=0.8848(3)nmandZ=I.TheX—rayanalysis revea1sthatthetw0kindsofcoordinatedcationsarelinkedbythreesharedcoordinatedwatermolecules,andK cati0nsc00rdinatewithtenoxygenatoms:fiveofwhichcomefromVloO286一 anion,theotherfivefromwater molecules.Thetitlecompoundexhibitsextended2DarraybuildingupofVloO286一 groupsconnectedbyten— c00rdinatedK+cati0ns.ThehexahydratednickelcationsNi(H20)62lieinneatappositiontothreeadjacentVloO2 clusters.CSD:413271 Keywords:decavanadatesynthesis2DlayeredstructureX'rayc~stalstructure 0Introduction Duringthepastdecades,polyoxometalateshave receivedextensiveattentionduetotheirapplications incatalysis.medicineandmaterialsciencesI.Poly— oxovanadateclustersareoneoffociofpolyoxometa— latechemistry.Becauseoftheirfascinatingstructures andpotentialapplications,theinorganic—organicself- assemblycompoundsbasedondecavanadatesbuilding blockshavebeensynthesizedextensivelyI,.Howev一 收稿Et期:2004.02.06.收修改稿Et期:2004-05-07. 国家自然科学基金资助项目(No.20071008). ?通讯联系人.E-mail:liusx@nenu.edu.cn 第一作者:李德慧,女,25岁,硕士研究生;研究方向:多酸合成化学. er,uptonow,thereportsaboutthedecavanadates containingtransitionmetalsarerarerelatively.Toour bestknowledge,typicalexamplesincludeK2Zn2VloO28? 16H20【I6】,Ca3VloO28?17H2007],Nd2Vl0028?28H20【I8J, Y2VloO28?24H2O【19J,La2Vl0028?20H20,Na6Vl0028. 18H2O[211,Er2VloO28?25H20[221,Sr3V1oO28?22H20【23], Ca2(H3O)2Vl0028?16H2OP41,【Ni(H2o)612[Na(HzO)4]z[V,0028] ? 3H2O,Ni(H2o)612[Na(H2O)3]2IVl0028]?4H2O,K,Na2 『Vl0028]?10H20[271,Cu3VloO28?24H20【28],CuNa4Vl0028' 第9期李德慧等:二维层状结构十钒酸盐[K(H:0):Ni(H:o)6]~Ivo0的合成及性 质?1077? 23H201嚣,K2[Co(H2O)6]2vloo28?4H20[:91,Cs4[Na2(H2O)1o] VloO283o/andNa[HVloO28]?10H20[311.Thiskindof polyoxometalatescompoundsisveryimportantinthe fieldsofcatalysis,medicineandmaterialsciences.In thispaper,wereportedthesynthesisandcrystal structureofanoveldecavanadates,[K(H2O)2Ni(H2O)6]2 [V】oO28].Thecompoundexhibitsextended2Darray buildingupofVloO28groupsconnectedbyten—coor— dinatedKcationsalongbcplane.Thecompoundis expectedtopresentnewapplications. 1Experimental 1.1MaterialsandMethods Allchemicalswereusedaspurchasedwithout furtherpurification.ElementalanalysesforK.Niand VweredeterminedusingaPLASMA—SPEC(I)ICP atomicemissionspectrometer.IRspectrumwas recordedintherangeof400-4000am一onanAlpha Centaurt/IRspectrophotometerusingKBrpellets. VNMRwascamedoutonaBrukerAC.500spec. trometerwithCDCN,VOClasanexternalreference f0rchemicalshifts. 1-2Preparationof【K(H2o)2Ni(H20)6]2【V~002s] Thetitlecompoundwassynthesizedasbrown blocksin46%yieldsbasedonVbyroutineprocess. 2.0gofKVOwassolvedin50mLwarmdistilled water.ThesolutionwastreatedwithNiSO4dropwise withstirring.Thenthemixturewasadjustedtoabout pH4withH2SO4.Thecolorofthesolutionchanged intoorangewiththeadditionofH2SO4.Themixture waskeptstirredwhilereactionproceeded.Afterthree hours.theresultingsolutionwasfilteredandlefttoe. vaporateatroomtemperature.Browncrystalsuitable forX?-raycrystallographywasobtainedbyslowevapo?- rationatroomtemperatureinairaftertendays.Ana1. calc.(%)forK2Ni2IVlo028]?16H2O:K,5.43;Ni,8.14; V,35.34;Found(%):K,5.42;Ni,8.16;V,35.37. 1.3X.rayStructureDetermination Abrownsinglecrystalwithdimensions0.421 mmx0.374mmx0.215mmwasmountedinsidea glassfibercapillary.DatawerecollectedonaRigaku R.AXISRAPIDIPdiffractometerwithMoKaradia. tion(A=0.071073nm)at293Kintherange2.04.< 0<27.48..Atotalof6367reflectionsweremeasured, ofwhich4008wereindependentreflections.ft= 0.0557).Empiricalabsorptioncorrection(scan) wasapplied.Theintensitydatawerecorrectedfor Lorentz—polarizationfactors.Thestructurewassolved bythedirectmethodusingSHELX97programand refinedbythefull—matrixleast—squaresmethodon. Hydrogenatomswereplacedgeometrically.Allthe non—hydrogenatomswererefinedanisotropically.The finalcycleofthefull?-matrixleast?-squaresrefinement convergedwithun—weightedandweightedagreement factorsofR=?III—Ill/II,toR2={?(一2】/ ?(2)2]}(w=l/[tr(确+(O.1547P)+0.00P])where (Fo+2ec~9/3).ThefinalRl=O.0521andfoR2=O.1617. Theselectedbondlengthsandangleswithassociated standarderrorsarelistedinTables1. CSD:413271 2ResultandDiscussion 2.1IRSpectrum TheIRspectrumof[K(H2O)2Ni(H2o)d2ivloo28]is showninFig.1.Inthespectrum,thebandat961cm一 isascribedtothestretchingvibrationoftheterrainal V.0bonds.Thepeaksat839and748am一arechar- acteristicbandsofbridgingasymmetricvibrationsof V.O.Vwhilethesymmetriconesareat581and525 am,.Thestrongfeatureat3385am一isassignedto thestretchingvibrationofO—Hbondinwater molecu】es. wavenumbcr/cm Fig.1IRspectrumof[K(H20)2Ni(H20)6l2【V100 2.2IVNMRSpectrum Therearethreetypesofvanadiumatomsaccord— ingthecoordinationenvironmentinthedecavanadate clusterwiththeratioof4:4:2(seeDescriptionofthe ? 1078?无机化学第2O卷 Table1SelectedBondLengths(哪)andAngles(.)forKzNi2[VID0盈】?16HzO V(1)一O(19) V(1)一O(18) V(1)?0(20) V(1)一O(12) V(1)一O(11) V(1)一0(21) V(4)一O(1) V(4)一o(20) V(4)一0(15) V(4)?0(141 V(4)一0(16) V(4)?0(21) K(1)一O(W2) K(1)一O(W7) K(1)一0(33 K(1)一O(W8) 0(20)一V(1)一0(12) O(18)一V(1)一O(11) O(19)一V(1)一0(21) o(w8)?Ni(1)?O(W6) O(W7)?Ni(1)?o(w6) o(w4)一Ni(1)一O(W6) o(w3)一Ni(1)一O(W7) O(W8)一Ni(1)一O(W5) 0.1598(3) 0.1831(3) 0.1843(3) 0.1907(3) 0.2054(3) 0.2302(3) 0.1607(3) 0.1827f3) 0.1832(3) 0.1982(3) 0.2005(3) 0.2240(3) o.2753(4) 0.2920(4) o.3021(3) 0.3255(4) 154.31(12) 156.66(12) 174.88(14) 85.83(14) 87.79(12) 90.16(13) 91.71(141 175.45(14, V(2)一0(3) V(21?O(18) V(2)一0(15) V(2)一0(17) V(2)一0(131 V(2)一0(21) V(5)一0(11) Vf5)一O(13) V(5)一0(14) V(5)一0(16) V(5)?0(21) V(5)一0(21)#1 K(1)一0(2)#2 K(1)一0(19) K(1)一0(1)#4 0(15)一V(2)一0(17) O(18)一V(2)一0(131 0(3)一V(2)一0(21) o(w8)一Ni(1)一O(W7) O(W7)一Ni(1)?O(W5) o(w3)一Ni(1)一O(W4) o(w5)?Ni(1)一O(W6) O(W4)?Ni(1)?O(W7) 0.1601(3) 0.1838f3) 0.1872(3) 0.1889(3) 0.2021(3) 0.2333(3) 0.1684(3) 0.1706(3) 0.1899(3) 0.1932(3) 0.2115(3) 0.2127(3) 0.2777(3) 0.2985(3) 0.3044(3) 154.24(11) 155.61(12) 176.57(15) 86.71(131 88.86(13) 90.52(14) 92.94(13) 175.75(131 V(3)一0(2) Vf3)?0(12) V(3)?0(17) V(3)?0(14) V(3)?0(161 V(3)一0(21) Ni(1)?O(W3) Ni(1)一O(W8) Ni(1)一O(W4) Ni(1)一O(W7) Ni(1)一O(W5) Ni(1)一O(W6) K(1)一0(2o) K(1)一O(W6) K(1)一O(W1) 0(2)一V(3)一0(21) 0(1)?V(4)?0(21) 0(11)?V(5)一0(13) O(W4)一Ni(1)一o(w5) O(W3)一Ni(1)一o(w5) O(W3)一Ni(1)?o(w8) o(w8)?Ni(1)?O(W4) O(W3)?Ni(1)一O(W61 0.1605(3) 0.1814f3) 0.1837(3) 0.1999(3) 0.2012(3) 0.2222(3) 0.2038(3) 0.2039(3) o.2056(3) 0.2060(3) o.2069(3) 0.2071(3) 0.2777(3) 0.2996(4) 0.3112(4) 173.82(12) 173.75(12) 107.36(14) 87.52(13) 89.89(15) 91.30(161 96.86(13) 177.11(14) Symmetrytransformationsusedtogenerateequivalentatoms:#1:-x+1,-y+2,-z+2;#2:,y-1,; #3:-x+l,-y+1,-z+3 #4:-x+1,叫+1,-z+2. crystalstucturebelow).VNMRspectrumofthetitle compoundshowsthreeresonancesat-528,一508,一423 - 400-500-600 Fig.2VNMRspectrumof【K(H20)2Ni(H2O)612[Vl00 inCD3CN withthearearatioof2:2:1.I'heresultresembleV NMRspectrumofotherdecavanadatepolyanion【32】. 2.3CrystalStructureoftheCompound ThetitlecompoundconsistsoftwoNi(H2oVcati— ons,twoKcations,oneVloO286--group,andfouraddi? tionalwatermolecules.Theyareheldtogetherinthe crystalbyelectrostaticforcesandhydrogenbonds.As shownintheFig.3,Niatomsarecoordinatedtosix watermoleculestoformnearlyregularoctahedrathat lieinneatappositiontothreeadjacentVloO286-groups, sharingtwoorthreehydrogenbondswitheach.The distancesofOW…Oaverage0.2789am.InsuchOC— tahedra,theanglesofc/s—O—Ni—Oareintherange 85.83.-96.86.whiletheanglesoftrans一0一Ni?Orange from175.45.to177.1l..ThebonddistancesofNi—O areintherangeof0.2038-0.2071nm.TheKcations 第9期李德慧等:二维层状结构十钒酸盐[K(H20)zNi(H0)6]zIV00的合成及性 质?1079? Fig.3Structurefor【K(H2O)2Ni(H20)6]2【VJ0028】showingthe labelingofatoms areirregularlycoordinatedtotenoxygenatoms,five fromthreeneighboringV1o028clusters,threewater moleculesofonefaceoftheadjacentNi(H20)6group, andtwoadditionalwatermolecules.ThetenK—Odis— tancesaverage0.2964nm.whichisshorterthanthe correspondingonespreviouslyreported_l81. Thecentrosymmetricdecavanadatepolyanion VloO一ismadeupoftenVO6octahedrasharing edges.TherearesixVO6octahedraarrangedina2~3 equatorialplanebysharingedgeswitheachother,two aboveandtwobelowtheequatorialplanesharing slopingedgeswiththecentralsixVO6octahedra,dis. playingacage—likestructure. Inthedecavanadatecluster,theoxygenatoms canbevariouslyassembled:from(1)O:thehexaco— ordinated0(21)inthecenteroftheV6octahedra;(2) Ob:thetriply—bridging(0(14)and0(16))and(3)O: thedoubly—bridging(O(11),O(12),0(13),0(15),0 (17),O(18)andO(20))lyingonthesurfaceofthe [V1o028】6_cluster,to(4)Od:theterminalones(0(1),0(2), 0(3),0(19))lyingontheouterco1Tiers.Accordingto thepositionintheV100286一clusterandcoordination environment,thetenvanadiumatomscanbedivided intothreetypes:(1)V(1)andV(2),atthecornerof theequatorialplane,arebondedtooneO,fourOand oneOd;(2)V(3)andV(4)arelocatedaboveandbelow theequatorialplaneandbondedtooneO,twoOh, tWOOandoneOd;(3)v(5)isinthecenterofthee— quatorialplanewhichisbondedtotwoO,twoOhand twoO.Thefirsttwotypesofvanadaiumatoms,V(1), V(2),V(3)andV(4),formoxovanadium(V),i.e.VO,+, with0(19),0(3),0(2)andO(1),respectively.The thirdtypeofvanadiumatom,V(5),hastwoshortV—O bondswith0(11)and0(13)(0.1684and0.1706nm) andthebondangle0(11)一V(5)一0(13)is107.36..This groupwithabentconfigurationmightbeconsidered asaseparatedioxovanadium(V)ionsorthepervanadyl ionVO.AnexaminationoftheV—Obonddistances (Table1)showsthatV—Odbondsarerathershort,in therageof0.1598-0.1607nm.implyingsubstantial doublebonding.Twoshortdistancesf0.1684and 0.1706nm)areobservedinthedioxovanadium) moietiesbetweenv(5)and0(11),0(13)atoms.Ascan beseenfromthesedata,thevanadiumatomsarenot inthegeometriccenteroftheoctahedrabuttheyare closertothevertexoccupiedbytheterminaloxygen atomsforV(1),V(2),V(3)andV(4),andtotheone edgeoftheoctahedraforV(5).Thereforeallvanadium atomsarenotinthegeometriccenteroftheoctahedra. Inthetitlecompound,V1006一groupsarelinked throughten—coordinatedKcationstoformanextend— ed2Dmoleculararray,asshowninFig.4,EachK cationsCO0rdinatedtotwowatermoleculesisfurther bondedtothetwoaxialterminaloxygenatomsofa decavanadateclusterinabidentatefashion,oneequa— torialterminaloxygenatomandonedoubly—bridging oxygenatomofaseconddecavanadateclusterandone equatorialterminaloxygenatomofathirddecavana— datecluster.ThuseachV10028一clusterislinkedby sixten—COOrdinatedKcationstoformatwo—dimen— sionallayeredstructurealongbc—plane.Thehexahy— dratednickelcationsNi(H20)62areplacedaboveand belowthemoleculararraystocompletethecrystallat— tice. Fig.42Dlayeredstructurefor[K(H20)2Ni(H20)6]2[V,oO2s] alongbc—plane ? 1080?无机化学第20卷 References [1】MizunoN.,MisonoM.Chem.Rev.,1998,98,199. [2】CoronadoE.,Gomez-GarciaC.J.Chem.Rev.,1998,98,273. [3】MiillerA.,PeterF.Chem.Rev.,1998,98,239. [4】RhuleJ.T.,HillC.L.,JuddD.A.,SchinaziR.F.Chem.Rev., 1998,98,327. [5】NakamuraS.,OzekiT.Chem.Soc.,DahonTrans.,2001, 472. 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