【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
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