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Journal of Coordination Chemistry
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http://www.tandfonline.com/loi/gcoo20Design, synthesis and structure of
uranyl coordination polymers from 2-Dlayer to 3-D network structure
Si Yue Wei, Feng Ying Bai, Ya Nan Hou, Xiao Xi Zhang, Xue TingXu, Ji Xiao Wang, Huan Zhi Zhang & Yong Heng Xing
a
a
a
c
a
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b
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College of Chemistry and Chemical Engineering, Liaoning NormalUniversity, Dalian, PR China
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College of Life Sciences, Liaoning Normal University, Dalian, PRChina
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Click for updates Guangxi Key Laboratory of Information Materials, GuilinUniversity of Electronic Technology, Guilin, PR China
Accepted author version posted online: 27 Nov 2014.Publishedonline: 02 Jan 2015.
To cite this article: Si Yue Wei, Feng Ying Bai, Ya Nan Hou, Xiao Xi Zhang, Xue Ting Xu, JiXiao Wang, Huan Zhi Zhang & Yong Heng Xing (2015) Design, synthesis and structure of uranylcoordination polymers from 2-D layer to 3-D network structure, Journal of Coordination Chemistry,68:3, 507-519, DOI: 10.1080/00958972.2014.992341To link to this article: http://dx.doi.org/10.1080/00958972.2014.992341PLEASE SCROLL DOWN FOR ARTICLE
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systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditionsDownloaded by [Lanzhou University] at 07:10 16 March 2015 JournalofCoordinationChemistry,2015
Vol.68,No.3,507–519,http://dx.doi.org/10.1080/00958972.2014.992341
Design,synthesisandstructureofuranylcoordinationpolymersfrom2-Dlayerto3-Dnetworkstructure
SIYUEWEI†,FENGYINGBAI‡,YANANHOU†,XIAOXIZHANG†,
XUETINGXU†,JIXIAOWANG†,HUANZHIZHANG§andYONGHENGXING*†
Downloaded by [Lanzhou University] at 07:10 16 March 2015 †CollegeofChemistryandChemicalEngineering,LiaoningNormalUniversity,Dalian,PRChina
‡CollegeofLifeSciences,LiaoningNormalUniversity,Dalian,PRChina
§GuangxiKeyLaboratoryofInformationMaterials,GuilinUniversityofElectronicTechnology,
Guilin,PRChina
(Received7January2014;accepted8October2014)
SolvothermalreactionofuranylacetateandsuccinicacidinDMFresultedinformationofthreeuranylcoordinationpolymers,[(UO2)4(μ2-OH)7(OH)6]·2(H2O)·(H3O)·4NH2(CH3)2(1),[(UO2)(μ2-OH)(OH)3]·2NH2(CH3)2](2),and[(DMF)2(UO2)(μ2-OH)4(UO2))](3).Theproductswerecharacterizedbyelementalanalysis,IRspectroscopy,X-raysinglecrystal,andpowderdiffraction.Structuralanalysisshowsthat1isalayer,2and3are3-Dnetworkstructures.
Keywords:Coordinationpolymer;Solvothermalreaction;Crystalstructure;DMFhydrolysis
1.Introduction
Uranylcompoundshaveattractedattentionforpotentialapplicationsinionexchange[1,2],protonconductivity[3],photochemistry[4,5],nonlinearopticalmaterials[6,7],catalysis[8],andespeciallyinenergyandthemilitary.Thedirectedassemblyofdiscretemoleculestobuildpolymericarraysisatopicofinterest,andcrystalengineeringprovidesatoolforrealizationofsuchtargets.Thepredictableself-assemblyoflow-dimensionalmoleculesintohigh-dimensionalframeworksthroughweakintermolecularinteractionssuchashydrogenbonds,weakvanderWaalsinteractions,andπ–πstackingisanimportantstrategyincrystal
*Correspondingauthor.Email:xingyongheng@lnnu.edu.cn©2014Taylor&Francis
508S.Y.Weietal.
Downloaded by [Lanzhou University] at 07:10 16 March 2015 engineering[9].Oxygenandnitrogen-containingorganiccompoundsareoftenusedtoconstructdiversestructuresandfunctionaluranylcompounds,providingthepossibilityofforminghydrogen-bondednetworkstructures.Insomecases,hydrogenbondslinkuranyldiscreteclusterstoformchains,layers,oreven3-Dnetworkstructures.
Design,synthesis,andstructuresofuranylcompoundscomposedofuranylcarboxylatessuchas[UO2)3(Hcit)2(H2O)3]·2H2O[10],uranylphosphonatesandcarboxyphosphonatessuchasCo2[(UO2)6(PO3CH2CO2)6(H2O)13]·6H2O[11],anduranylcurbit[n]urilssuchas[UO2(CB5)](ReO4)2·2H2Oand[s2(CB5)(H2O)2][(UO2)2(HCOO)(OH)4]2·3H2O[12]havebeendescribed.However,studiesofuranylcoordinationpolymerswithsolventsasligandsarerare.TheUO22þspecieswithinactiveU=Odoublebondsgenerallyiscoordinatedonlythroughequatorialligands,yieldinginfinitechainsorsheets,while3-Dframeworkstruc-turesareformedoccasionally.Inthiswork,threeuranylcoordinationpolymershavebeen
þ
synthesized.Weemployacommonligand(DMF)toconnectUO22toformuranylpoly-mersfrom2-Dlayerto3-Dnetworkstructures.DMFcanbeusedasasolventandacoordi-natedligand.DMFiseasilyhydrolyzed,producingNH2(CH3)2+instrongacid,strongbase,orhightemperature[13].Inthispaper,weusethesepropertiesofDMFhydrolysisandcoordinationtoconstructthreeuranylcoordinationpolymers,[(UO2)4(μ2-OH)7(OH)6]·2(H2O)·(H3O)·4NH2(CH3)2(1),[(UO2)(μ2-OH)(OH)3]·2NH2(CH3)2](2),and[(DMF)2(UO2)(μ2-OH)4(UO2))](3).
2.Experimental
2.1.Materialsandmethods
IRspectrawererecordedonaJASCOFT/IR-480PLUSFouriertransformspectrometerwithpressedKBrpelletsfrom200to4000cm–1andaBrukerAXSTENSOR−27FTIRspectrometerwithKBrpelletsfrom4000to400cm−1.ElementalanalysesforC,H,andNwerecarriedoutonaPerkinElmer240Cautomaticanalyzer.X-raypowderdiffraction(PXRD)patternswereobtainedonaBrukerAvance-D8equippedwithCuKαradiation(λ=1.54183Å),intherange5°<2θ<50°,withastepsizeof0.02°(2θ)andacounttimeof2sperstep.2.2.Synthesis
Allchemicalspurchasedwereofreagentgradeorbetterandusedwithoutpurification.Caution!Whiletheuraniumcompoundusedinthesestudiescontaineddepleteduranium,precautionsareneededforhandlingradioactivematerials,andallstudiesshouldbeconductedinalaboratorydedicatedtostudiesofradioactivematerials.
2.2.1.Synthesisof[(UO2)4(μ2-OH)7(OH)6]·2(H2O)·(H3O)·4NH2(CH3)2(1).AmixtureofUO2(CH3COO)2·2H2O(0.0326g,0.0769mM)andsuccinicacid(0.0290g,0.25mM)inDMF(4mL)wasstirredfor1hatroomtemperature,thenthepHadjustedto7bysolu-tionofsodiumhydroxide(1M).Themixturewasintroducedintoareactionkettleandheatedstaticallyat160°Cforthreedays.Resultinglightyellowproductwasthenfiltered
Uranylcoordinationpolymers509
off,washedwithwater,anddriedinair.Anal.CalcdforC8H52N4O24U4(%):C,6.23;H,3.36;andN,3.64.Found(%):C,6.20;H,3.29;andN,3.69.
2.2.2.Synthesisof[(UO2)(μ2-OH)(OH)3]·2NH2(CH3)2](2).Thepreparationissimilartothatof1exceptthatthetemperaturewaschangedto100°CandpHadjustedto2bysolutionofnitricacid(1M).Yellowcrystalsof2wereobtainedafterwashingbywaterseveraltimes.Anal.CalcdforC4H20N2O6U(%):C,11.2;H,4.65;andN,6.51.Found(%):C,11.0;H,4.61;andN,6.42.
2.2.3.Synthesisof[(DMF)2(UO2)(μ2-OH)4(UO2))](3).Thepreparationissimilartothatof1exceptthatthetemperaturewaschangedto80°C.Yellowcrystalsof3wereobtainedafterwashingbywaterseveraltimes.Anal.CalcdforC6H18N2O10U2(%):C,9.55;H,2.39;andN,3.71.Found(%):C,9.44;H,1.94;andN,3.60.2.3.X-raycrystallographicdetermination
Asinglecrystalwithdimensions0.58mm×0.34mm×0.18mmfor1wasselectedforstructuredetermination.ReflectiondatawerecollectedatroomtemperatureonaBrukerAXSSMARTAPEXIICCDdiffractometerwithgraphitemonochromatedMo-Kαradiation(λ=0.71073Å)from1.87<θ<25.00°.Atotalof20,048(4303unique,Rint=0.0456)reflectionsweremeasured.Thestructureof2wasdeterminedbysinglecrystalX-raydif-fraction.Ayellowsinglecrystalof2withdimensions0.50mm×0.34mm×0.18mmwasmountedonaglassfiber.ReflectiondatawerecollectedatroomtemperatureonaBrukerAXSSMARTAPEXIICCDdiffractometerwithgraphitemonochromatedMo-Kαradiation(λ=0.71073Å)from2.17<θ<25.00°.Atotalof4612(1941unique,Rint=0.0575)reflec-tionsweremeasured.In2,thelargestdiff.peakandholeare7.418and−4.975eÅ–3andthemajorresidualpeaksappeararoundU(U1–Q1andU1–Q2bondlengthsare0.883and0.902Å).
Thestructureof3wasdeterminedbysinglecrystalX-raydiffraction.Ayellowsinglecrystalof3withdimensions0.44mm×0.38mm×0.13mmwasmountedonaglassfiber.ReflectiondatawerecollectedatroomtemperatureonaBrukerAXSSMARTAPEXIICCDdiffractometerwithgraphitemonochromatedMo-Kαradiation(λ=0.71073Å)from2.17<θ<25.00°.Atotalof9043(3637unique,Rint=0.0362)reflectionsweremeasured.In3,thelargestdiff.peakandholeare7.133and−1.398eÅ–3andthemajorpeaksappeararoundU(U1–Q1andU2–Q2bondlengthsare0.829and0.811Å).Empiricalabsorptioncorrectionswereappliedusingmulti-scantechnique.Allabsorptioncorrectionswereper-formedusingSADABS[14].Crystalstructuresweresolvedbydirectmethods.Allnonhy-drogenatomswererefinedwithanisotropicthermalparametersbyfull-matrixleast-squarescalculationsonF2usingSHELXL-97[15].Hydrogensoncarbonandnitrogenwerefixedatcalculatedpositionsandrefinedusingaridingmodel,butthehydrogensoflatticewatermoleculein1werefoundinthedifferenceFouriermap.Thehydrogensoftheμ2-O(O3,O5,O6,O10for1;O3for2;O3,O4,O5,O8for3)andtheU–Otfromterminalhydroxoions(O4,O9,O14for1;O4,O5,O6for2)werenotlocated.Crystaldataanddetailsofthedatacollectionandthestructurerefinementaregivenintable1.Selectedbonddistancesandanglesaregivenintable2.FiguresanddrawingsweremadewithDiamond3.2.
Downloaded by [Lanzhou University] at 07:10 16 March 2015 510
Table1.
Crystaldataof1–3.
1
S.Y.Weietal.
Complexes
Formula
FormulaweightCrystalsystemSpacegroupa(Å)b(Å)c(Å)α(°)β(°)γ(°)V(Å3)Z
DCalcd(gcm−3)Crystalsize/mmF(000)
μ(Mo-Kα)/mm−1θ(°)
Reflectionscollected
Independentreflections[I>2σ(I)]ParametersGoodnessoffitRawR2aab2
C4H20N2O6U430.25MonoclinicC2/c
13.620(4)8.709(2)19.604(5)90
100.957(4)90
2283.0(10)82.503
0.50×0.34×0.18158414.2242.79–24.994612
1941(1687)1231.1
0.0877(0.0950)b0.2461(0.2546)b3
C6H18N2O10U2754.28MonoclinicC2/c
23.848(2)7.3947(7)17.0358(16)90
97.690(2)90
2977.3(5)83.366
0.44×0.38×0.13265621.7771.72–28.379043
3637(2856)1851.045
0.0390(0.0565)b0.0948(0.1021)bDownloaded by [Lanzhou University] at 07:10 16 March 2015 C8H52N4O24U41540.66
OrthorhombicPnma
17.0296(13)22.1116(17)9.0134(7)909090
3394.0(5)43.015
0.58×0.34×0.18275219.1141.84–28.3420,0484303(3615)1981.030
0.0427(0.0535)b0.1079(0.1134)bR=ΣêêFoê−êFcêê/ΣêFoê,wR2={Σ[w(Fo2−Fc2)2]/Σ[w(Fo2)2]}1/2;[Fo>4σ(Fo)].Basedonalldata.
3.Resultsanddiscussion3.1.Synthesis
UO2(CH3COO)2·2H2Oandsuccinicacidwereusedasstartingmaterialswhileasolvother-malsynthesisassistedbyDMFwasadoptedtopreparetheuranylcomplexes.Originally,weaddedsuccinicacidtothesystemtoobtainauraniumcoordinationpolymerwithcar-boxylicacids[16],unfortunately,reactionresultsshowthatthesuccinicacidisnotcoordi-natedwithuranyl,andprotonatedNH2(CH3)2+cation,whichisproducedbyDMFhydrolysisthatconnectswithuranylbyhydrogenbondsorDMFdirectlycoordinatedwithuranyl.Whensuccinicacidwasnotaddedinthesyntheticsystem,wedonotobtain1–3.Thus,theadditionofthesuccinicacidisnecessaryinthereaction.Inthereactions,simi-larly,pHisalsoessentialtothepolymerizationofuranyl.IsolatedUO22þcationsexistinaqueoussolution(pH<2.5).However,inlessacidicmedia,theidentityofuranylspeciesvarieswiththeconcentrationofOH−(aq)ions[17].WhenpH>2.5,UO22þtendstohydro-lyzeandpolymerize,forminganumberofpolynuclearuranylspecies,andthengeneratecomplexprecipitates,suchasU2O52þandU3O82þ[17].Themainfactorswhichinfluence
þ
thehydrolysisaretemperatureandtheconcentrationofUO22þ.TheprocessofUO22hydrolysisisshownbelow:
Uranylcoordinationpolymers
Table2.
Selectedbonddistances(Ǻ)andangles(°)for1–3.*
1.774(7)2.251(5)1.772(9)1.774(9)2.256(5)157.1(2)178.3(4)91.1(3)89.7(3)90.3(3)179.1(4)91.2(3)1.793(13)2.364(11)177.3(7)151.5(5)178.2(4)89.7(7)146.1(4)1.747(7)2.324(6)2.332(5)1.746(7)2.323(6)2.382(8)179.2(4)92.6(3)90.4(3)141.33(15)33.24(15)91.2(3)88.3(3)91.5(3)91.5(3)
O(2)–U(1)O(6)–U(1)O(9)–U(2)O(12)–U(3)U(1)–O(6)–U(3)O(1)–U(1)–O(6)O(2)–U(1)–O(6)O(7)–U(2)–O(9)#2O(8)–U(2)–O(10)O(11)–U(3)–O(13)#2O(12)–U(3)–O(10)U(1)–O(2)U(1)–O(5)
O(2)–U(1)–O(4)O(1)–U(1)–O(3)O(6)–U(1)–O(3)#1O(5)–U(1)–O(6)O(6)–U(1)–O(3)U(1)–O(2)U(1)–O(5)#1U(1)–U(1)#1U(2)–O(7)U(2)–O(8)#3U(1)–U(1)#2O(1)–U(1)–O(4)O(1)–U(1)–O(5)#1O(4)–U(1)–O(5)O(4)–U(1)–U(1)#2O(10)–U(2)–U(2)#3O(7)–U(2)–O(4)O(4)–U(2)–O(8)O(4)–U(2)–O(10)O(7)–U(2)–O(9)
1.767(7)2.289(5)2.258(5)1.769(9)161.4(3)90.3(3)90.3(3)90.8(3)89.8(4)91.2(3)88.1(4)1.792(12)2.244(11)92.4(6)90.5(6)136.8(4)73.9(4)72.3(4)1.755(8)2.325(5)3.9199(4)1.752(7)2.331(6)3.9199(4)87.8(3)89.1(3)77.7(2)109.96(16)104.07(19)89.7(3)138.6(2)150.5(2)89.6(3)
O(3)–U(1)O(7)–U(2)O(10)–U(2)O(10)–U(3)U(2)–O(10)–U(3)O(4)–U(1)–O(3)O(4)–U(1)–O(6)O(7)–U(2)–O(8)O(9)–U(2)–O(10)O(13)–U(3)–O(10)O(10)–U(3)–O(6)U(1)–O(4)U(1)–O(6)
O(4)–U(1)–O(5)U(1)–O(3)–U(1)#1O(1)–U(1)–O(4)O(4)–U(1)–O(3)O(5)–U(1)–U(1)#1U(1)–O(4)U(1)–O(5)U(1)–U(1)#2U(2)–O(4)U(2)–O(10)U(2)–U(2)#3O(2)–U(1)–O(4)O(4)–U(1)–O(5)#1O(2)–U(1)–O(3)#2O(3)–U(1)–U(1)#2O(6)–U(2)–O(7)O(6)–U(2)–O(8)O(6)–U(2)–O(10)O(8)–U(2)–O(10)O(8)–U(2)–O(9)
511
Complex1O(1)–U(1)O(4)–U(1)O(8)–U(2)O(11)–U(3)O(13)–U(3)U(1)–O(3)–U(2)O(2)–U(1)–O(1)O(2)–U(1)–O(4)O(2)–U(1)–O(5)O(8)–U(2)–O(9)O(12)–U(3)–O(11)O(11)–U(3)–O(13)
2.298(5)1.767(9)2.296(7)2.313(7)146.9(4)76.17(19)154.87(19)178.7(4)143.38(14)141.76(14)68.98(13)2.235(12)2.323(10)77.7(5)115.5(4)92.4(6)136.1(5)178.2(4)2.290(6)2.327(5)3.9199(4)2.291(6)2.377(7)3.8961(8)91.5(3)140.9(2)90.7(3)173.89(13)178.7(4)90.4(3)88.2(3)70.9(2)145.7(3)
Downloaded by [Lanzhou University] at 07:10 16 March 2015 Complex2U(1)–O(1)U(1)–O(3)
O(1)–U(1)–O(2)O(4)–U(1)–O(6)O(5)–U(1)–U(1)#1O(2)–U(1)–O(5)O(5)–U(1)–O(3)Complex3U(1)–O(1)U(1)–O(3)U(1)–O(3)#2U(2)–O(6)U(2)–O(8)U(2)–O(9)
O(1)–U(1)–O(2)O(1)–U(1)–O(3)O(1)–U(1)–O(5)O(3)–U(1)–O(3)#2O(8)–U(2)–U(2)#3O(6)–U(2)–O(4)O(7)–U(2)–O(8)O(7)–U(2)–O(10)O(6)–U(2)–O(9)
*Symmetrycodes:#1:−x,1−y,2−z;#2:x,1.5−y,zfor1;#1:1.5−x,0.5−y,1−zfor2;#1:−x+y,0.5−y,1−z;#2:0.5−x,0.5+y,0.5−z;#3:0.5−x,−0.5+y,0.5−zfor3.
Underhighlyacidicconditions,themonomericUO22þcationdirectlytakespartincrystalgrowth(suchas2).AbinuclearmodelofuranylcomplexwascomposedunderpH7andsolvothermalconditions,andthebinuclearspecieswithuraniumcoordinationtoDMF(suchas3).Fortrinuclear(UO2)3(μ2-OH)5+,thespeciesmayloseawatertoformaoxo-hydroxo-uraniumpolyhedralcation,(UO2)3O(μ2-OH)3+[18].IntherelativelyhighpHvalues,oligomericuranylspeciesareformedandsubsequentlyinvolvedincrystallizationofuranylcomplex.
3.2.Crystalstructureanalysis
3.2.1.Crystalstructureof1.Complex1crystallizesintheorthorhombicsystemwithPnmaspacegroup.Selectedbonddistancesandanglesof1aregivenintable2.X-raysinglecrystalanalysisindicatesthattheasymmetricunitof1ismadeupoftwoUO22þ
512S.Y.Weietal.
Downloaded by [Lanzhou University] at 07:10 16 March 2015 Figure1.ThecoordinationenvironmentofUin1(hydrogensomittedforclarity).Symmetrycodes:#1:−x,1−y,2−z;#2:x,1.5−y,z.
cations,threeandahalfhydroxobridgegroups,threeterminalhydroxoions,twofreeprotonatedNH2(CH3)2+cations,afreewater,andahalfprotonatedwater(H3O+).O1WisprotonatedwaterandO2Wiswatermolecule.FromthecoordinationenvironmentofU(figure1),thethreeuraniumionsareallseven-coordinate.TheU1centeriscoordinatedwithsevenoxygens(O1,O2,O3,O4,O5,O5#2,andO6;#2:−x,1−y,1−z)toformapentagonalbipyramidgeometry,O1andO2areterminaloxygens,O4isfromterminalhydroxoions,andO3,O5,O5#2(#2:−x,1−y,1−z),andO6arehydroxobridgeatoms.Throughhydroxobridgeatoms(O3andO6),U1isfurtherconnectedwithU2andU3,respectively.U2andU3areconnectedbyhydroxobridge(O10).U1,U2,U3,O3,O6,andO10areself-assembledtoformatwistysix-memberring.U2isbondedwithsevenoxygens(O3,O7,O8,O9,O10,O3#1,O9#1,#1:x,1.5−y,z)withO7andO8terminal,O9andO9#1arefromterminalhydroxoions,andO3andO3#1(#1:x,1.5−y,z)arehydroxobridgestogenerateapentagonalbipyramidgeometry.ThecoordinationenvironmentsofU2andU3arequitesimilar,exceptthatthepairofterminalhydroxogroupsoneachUcenter(adjacentinthepentagonalplane)isdifferent.TheO9⋯O9#1separationonU2is2.69Å,whereasthecorrespondingseparationbetweenterminalhydroxogroupsonU3
Figure2.A1-Dchainnetworkstructureof1.
Uranylcoordinationpolymers513
Downloaded by [Lanzhou University] at 07:10 16 March 2015 (O13···O13#1)is2.79Å.TheU=Obondlengthsrangefrom1.756(10)to1.789(12)Å,thebondlengthsofU–Otfromterminalhydroxoionsvaryfrom2.251(5)to2.258(5)Å,andthebondlengthsofU–Obfromhydroxobridgesvaryfrom2.248(5)to2.385(5)Å.TheaveragebondlengthofU–Obis2.325(5)Åwhichmatchesthatof2.33(3)ÅfromtheCSD,andisclosetothatreported[19](2.35(4)Å),butismuchshorterthanthecorrespondingbondlengthofU–OWfromcoordinationwater(2.406Å)[20].ThebondanglesofO=U=Orangefrom178.0(6)to179.6(6)°andthebondanglesofO–U–Ovaryfrom63.9(3)to157.0(4)°.
Inthepackingof1,fouradjacentO=U=Oareconnectedbyhydroxobridgestoformabuildingblockof(UO2)4(μ2-OH)9(OH)4.Thesetwoadjacentbuildingblocksfurthersharetwohydroxobridgesandexpandedalongthebaxistoforma1-Dchain.TherearestrongH-bondsbetweentheprotonsonnitrogenofthedimethylammoniumcationsandoxygenofthechain(figure2).ThehydrogenbondsareN2–H2D⋯O13,2.7244Å,167.00°;N2–H2E⋯O4,2.8667Å,148.00°;N2–H2E⋯O5,2.7943Å,133.00°,whileH2Eisthehydrogenofabifurcatedhydrogenbond.Furthermore,thechainismorestableinthepres-enceofthesehydrogenbonds.AdjacentchainsarefurtherconnectedbyC3–H3B⋯O1(3.2531Å,140.00°)toforma2-Dlayerstructure(figure3).
3.2.2.Crystalstructureof2.Complex2crystallizesinthemonoclinicsystemwithC2/cspacegroup.Selectedbonddistancesandanglesof2aregivenintable2.X-raysinglecrystalanalysisindicatesthat2ismadeupofonecrystallographicallyindependentUO22þ,onehydroxobridge,threeterminalhydroxoions,andtwoprotonatedNH2(CH3)2+cations.
Figure3.Aviewofhydrogen-bondinginteractionsof1.
514S.Y.Weietal.
Downloaded by [Lanzhou University] at 07:10 16 March 2015 U(VI)isseven-coordinate(figure4),O1andO2areterminaloxos,O4,O5,andO6originatefromterminalhydroxoions,andO3andO3#1(#1:1.5−x,0.5−y,1−z)arehydroxobridgesinapentagonalbipyramid.TheU=Obondlengthsrangefrom1.792(13)to1.793(13)Å.ThebondlengthsofU–Otfromterminalhydroxoionsvaryfrom2.235(12)to2.323(10)ÅandthebondlengthsofU–Obfrombridginghydroxogroupsrangefrom2.235(12)to2.383(11)Å.TheaverageU–Obbondlengthis2.374(11)Å,matchingthatof2.33(3)ÅfromtheCSD,andclosetothatreported[19](2.35(4)Å),butshorterthanthebondlengthofU–OW(2.406Å)reported[20].ThebondangleofO=U=Ois177.3(7)°andthebondanglesofO–U–Ovaryfrom64.5(4)to151.5(5)°.
Inthemolecularpacking,aclusterunit[(UO2)2(μ2-OH)2(OH)6]isconnectedbytwotypesofhydrogenbonds,N–H⋯OandC–H⋯O.TheyareN1–H1NA⋯O5,N1–H1NB⋯O6,N2–H2NA⋯O3,N2–H2NA⋯O4,N2–H2NB⋯O6,andC3–H3B⋯O6.Thehydrogenbondconnectingmodeisillustratedinfigure5.Twoadjacentclusterunits[(UO2)2(μ2-OH)2(OH)6]areconnectedbyhydrogenbonds(N2–H2NA⋯O4,2.9698Å,139.58°;N2–H2NB⋯O6,2.7317Å,169.98°)andexpandedtoformaninfinitechainalongthebaxis.Adjacentchainsarefurtherconnectedbytheclusterunitswithintermolecularhydrogenbonds(N1–H1NA⋯O5,2.5820Å,169.95°;N1–H1NB⋯O6,2.7679Å,169.34°)toforma3-Dnetworkstructure(figure6).
3.2.3.Crystalstructureof3.Complex3crystallizesinthemonoclinicsystemwithC2/cspacegroup.Selectedbonddistancesandanglesof3aregivenintable2.X-raysinglecrystalanalysisindicatesthat3ismadeupoftwoUO22þcations,fourhydroxobridges,andtwoDMFmolecules.U1andU2areseven-coordinate.Thetwodistincturanylions,U1andU2,havenearlylinear[O=U=O]2+bondanglesof179.3(4)and178.7(4)°,respec-tively.U1(VI)iscoordinatedbyO1andO2(U(1)–O(1),1.748(7)Å;U(1)–O(2),1.755(8)Å)fromterminaloxogroups,O3,O3#3,O4,O5,andO5#2(#2:0.5−x,0.5+y,0.5−z;#3:0.5−x,−0.5+y,0.5−z)fromhydroxobridgestoformapentagonalbipyramid.Similarly,U2(VI)iscoordinatedbyO6andO7(U(2)–O(6),1.749(7)Å;U(2)–O(7),1.751(7)Å)fromterminaloxos,O8andO8#1(#1:−x,y,0.5−z)fromhydroxobridges,andO9andO10fromDMF(U(2)–O(9),2.382(8)Å;U(2)–O(10),2.377(7)Å)toformapentagonal
Figure4.ThecoordinationenvironmentofUin2(hydrogensomittedforclarity).Symmetrycodes:#1:1.5−x,0.5−y,1−z.
Uranylcoordinationpolymers515
Downloaded by [Lanzhou University] at 07:10 16 March 2015 Figure5.Hydrogenbondsconnectingof2.
Figure6.Aviewofhydrogen-bondinginteractionsof2.
bipyramid(figure7).TheaveragebondlengthofU–ODMFis2.380(8)Å,closeto2.401(4)Åreported[16].BondlengthsofU–Obfrombridginghydroxogroupsvaryfrom2.290(6)to2.332(5)ÅandbondanglesO−U−Ovaryfrom119.0(10)to121.4(10)°.
516S.Y.Weietal.
Downloaded by [Lanzhou University] at 07:10 16 March 2015 Figure7.ThecoordinationenvironmentofUin3(hydrogensomittedforclarity).Symmetrycodes:#1:−x+y,0.5−y,1−z;#2:0.5−x,0.5+y,0.5−z;#3:0.5−x,−0.5+y,0.5−z.
ThereisahydrogenbondbasedonC–H⋯Ointheframeworkstructure,includingC3–H3B⋯O1,C6–H6A⋯O3,andC6–H6C⋯O7.TwoadjacentunitsUO2(μ2-OH))arecon-nectedbytwohydroxobridgesandexpandedalongthebaxistoforma1-Dchain.Parallelchainsarefurtherbridgedbybuildingblocksof[(OH)(DMF)2(UO2)(OH)2(UO2)(DMF)2(OH)]toforma2-DnetworkstructurewiththecoordinatedDMForientedaboveandbelowthemeanplaneofthenetwork(figure8).The2-Dnetworkstructureisfurtherconnectedbyhydrogenbonds(C3–H3B⋯O1,3.3869Å,170.86°;C6–H6A⋯O3,3.2948Å,144.60°;C6–H6C⋯O7,3.2677Å,138.78°)toforma3-Dnetworkstructure(figure9).3.3.IRspectroscopy
InIRspectra[figureS1(a)–(c),seeonlinesupplementalmaterialathttp://dx.doi.org/10.1080/00958972.2014.992341]ofthecomplexes,thebroadabsorptionsat3456,3376,and3442cm−1indicatethepresenceofN–HstretchingofDMF.Thebandsat2920,2912,and2943cm−1areattributedtothepresenceofasymmetricalC–H(CH3)stretches.Thebandsat1642,1633,and1655cm−1areattributedtobendingofN–H.Thebandsat1469–1363cm−1areassignedtoC–Hbending.Bandsat918,929,and923cm−1areassignedtotheU=Ostretch.TheFTIRspectraofthecomplexesareconsistentwiththestructuralanalyses;detailedassignmentoftheIRspectrafor1–3isshownintable3.3.4.X-raypowderdiffractionstudy
ThesimulatedandexperimentalPXRDspectraof1–3areshowninSupplementarymaterial(figuresS2–S4).TheexperimentalPXRDspectraaccordwiththesimulatedPXRDspectrum,indicatingthat1–3arepurephase,withoutimpurities.
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Downloaded by [Lanzhou University] at 07:10 16 March 2015 Figure8.A2-Dlayernetworkstructureof3viewedfromthea–bplane.
Figure9.Aviewofhydrogen-bondinginteractionsof3.
518
Table3.
S.Y.Weietal.
IRspectraof1–3.
1
345629201642
1469,1396918
23376291216331401929
3
344229431655
1435,1363923
ComplexesνNHν(CH3)δNHδC–HνU=O4.Conclusion
Wehavereportedthreeuranylcomplexes,[(UO2)4(μ2-OH)7(OH)6]·2(H2O)·(H3O)·4NH2(CH3)2(1),[(UO2)(μ2-OH)(OH)3]·2NH2(CH3)2](2),and[(DMF)2(UO2)(μ2-OH)4(UO2))](3).For1,thebuildingblock((UO2)4(μ2-OH)9(OH)4)issharedbytwohydroxobridgesandfurtherexpandedalongthebaxistoforma1-Dchain;adjacentchainsarefurtherconnectedbyhydrogenbonds(N–H⋯OandC–H⋯O)toforma2-Dlayer.For2,[(UO2)2(μ2-OH)2(OH)6]isconnectedbyhydrogenbonds(N–H⋯OandC–H⋯O)toforma3-Dnetworkstructure.For3,DMFismonodentateandconnectedbyhydrogenbonds(C–H⋯O)toforma3-Dnetworkstructure.Researchisinprogresswiththeaimofexploringtheuraniumcoordinationchemistrywithdifferentligandsandfurtherstudyoftheirproperties.
Supplementarymaterial
Tablesofatomiccoordinates,isotropicthermalparameters,andcompletebonddistancesandangleshavebeendepositedwiththeCambridgeCrystallographicDataCenter.CopiesofthisinformationmaybeobtainedfreeofchargebyquotingthepublicationcitationanddepositionnumbersCCDCfor1–3:979412,979413and979414,respectively,fromtheDirector,CCDC,12UnionRoad,Cambridge,CB21EZ,UK(Fax:+441223336033;Email:deposit@ccdc.cam.ac.ukorhttp://www.ccdc.cam.ac.uk).Acknowledgements
WethankNaturalScienceFoundationofChina[grantnumber21371086]andGuangxiKeyLaboratoryofInformationMaterials,GuilinUniversityofElectronicTechnology,PRChina(ProjectNo.1210908-06-K)forfinancialassistance.References
P.O.Adelani,T.E.Albrecht-Schmitt.Angew.Chem.,Int.Ed.,49,8909(2010).P.O.Adelani,T.E.Albrecht-Schmitt.Inorg.Chem.,50,12184(2011).
D.Grohol,M.A.Subramania,D.M.Poojary,A.Clearfield.Inorg.Chem.,35,5264(1996).K.E.Knope,C.L.Cahill.Inorg.Chem.,48,6845(2009).
Y.S.Jiang,Z.T.Yu,Z.L.Liao,G.H.Li,J.S.Chen.Polyhedron,25,1359(2006).K.M.Ok,J.Baek,P.S.Halasyamani,D.O’Hare.Inorg.Chem.,45,10207(2006).
S.Wang,E.V.Alekseev,J.Ling,G.Liu,W.Depmeier,T.E.Albrecht-Schmitt.Chem.Mater.,22,2155(2010).
[8]Z.L.Liao,G.D.Li,M.H.Bi,J.S.Chen.Inorg.Chem.,47,4844(2008).[1][2][3][4][5][6][7]
Downloaded by [Lanzhou University] at 07:10 16 March 2015 Uranylcoordinationpolymers519
Downloaded by [Lanzhou University] at 07:10 16 March 2015 [9]S.V.Kolotuchin,E.E.Fenlon,S.R.Wilson,C.J.Loweth,S.C.Zimmerman.Angew.Chem.Int.Ed.Engl.,34,
2654(1995).
[10]P.Thuéry.Chem.Commun.,8,853(2006).
[11]A.N.Alsobrook,B.G.Hauser,J.T.Hupp,E.V.Alekseev,W.Depmeier,T.E.Albrecht-Schmitt.Chem.
Commun.,46,9167(2010).
[12]P.Thuery.Cryst.GrowthDes.,8,4132(2008).
[13]J.Marrot,K.Barthelet,C.Simonnet,D.Riou.C.R.Chimie,8,971(2005).
[14]G.M.Sheldrick.SADABS,ProgramforEmpiricalAbsorptionCorrectionforAreaDetectorData,University
ofGöttingen,Göttingen(1996).
[15]G.M.Sheldrick.SHELXS97,ProgramforCrystalStructureRefinement,UniversityofGöttingen,Göttingen
(1997).
[16]J.L.Wang,Z.Y.Deng,S.B.Duan,Y.H.Xing.J.Coord.Chem.,65,3546(2012).
[17]D.L.Clark,S.D.Conradson,R.J.Donohoe,D.W.Keogh,D.E.Morris,P.D.Palmer,R.D.Rogers,C.D.Tait.
Inorg.Chem.,38,1456(1999).
[18]K.X.Wang,J.S.Chen.Acc.Chem.Res.,44,531(2011).[19]P.Thuery.Cryst.GrowthDes.,11,2606(2011).[20]P.Thuéry.CrystEngComm,11,1081(2009).
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