通过有机配体界定的锌的磷酸化合物拓扑结构(晶(7)

FanandHanson

Figure4.(a)Crystalstructureofcompound4withatomlabelingscheme.Thermalellipsoidsaredrawnat50%probability.(b)Polyhedralrepresentationofthe2Dsheetin4(Zn:blue.P:yellow).(c)Packingdiagramofcompound4.

arelocatedintheresiduale-densitymapandrefinedindependently.Thus,oneL2ligandin3playsthedualroleoftemplateandligandinthestabilizationofthestructure.Thechainsin3arelinkedtogetherbytheL2ligandstoformatwo-dimensional(2D)sheet.Thetetradentateligandcoordinatestothefourzincatomsofthetriplefused4-ring,andthebidentateligandcoordinatestothetwozincatomsofthe4-ring.TheprotonatedimidazolegroupsofthebidentateligandarehydrogenbondedtotheadjacentsheetsthroughinteractionwiththeP1group[(N7 O2))2.646-(5)Å,and(N7-H7B-O2))177°.]Thelayerstructureof3isheldtogetherviahydrogenbondinginanABABpatterntoformthe3Dstructure.Apackingdiagramfor3isprovidedintheSupportingInformation.

CrystalStructureof[Zn2(HPO4)2(C18H16N4)](4)and[Zn(HPO4)(C18H14N2)](5).Theasymmetricunitofcom-pound4containsacrystallographicallyindependentzincatom,aphosphategroup,andhalfofanL3ligand,asshowninFigure4a.EachzincatomistetrahedrallycoordinatedbythreeoxygensfromphosphategroupsandanitrogenfromL3[(Zn1-O)av)1.938Å,(O-Zn1-O)av)112.7°,and(O-Zn1-N)av)106.1°].EachphosphategroupcoordinatestothreezincatomsthroughP-O-Znlinkages[(P-O-Zn)av)129.0°].ThelongestP-Odistance[(P1-O1))1.569(3)Å]indicatesthattheterminaloxygen(O1)isan-OHgroup.

AsshowninFigure4b,theinorganicframeworkin4consistsofatwo-dimensionalnetworkconstructedfromedge-sharing4-ringsand8-rings,witha4.82topology.Twotypesof4.82patternsarecommonlyobserved:onewithelongated8-ringsinaherringbonepattern6handonewith8-ringsthatmorecloselyapproximateoctagons.10Itisevidentthatthe4.82patternof4haselongated8-rings.TheL3ligandadoptsacisconformationwithtwoimidazolegroupsextendingtothesamesideofthenaphthalenering.Thedihedralanglebetweentheimidazoleandnaphthaleneis82.0°.ThesheetsareconnectedbyL3ligandstoforma3Dstructure.Specifically,thesheetsarecovalentlypillaredbyL3ligandsasshowninFigure4c.Inzincphosphates/phosphitescontaining4.82-sheets,thelayerstructureisoftenpillaredbyligands,H-bonds,orZn-O-Plinkages.10,22Astrikingfeatureoftheinterlayerpillarsisthestackingoftheorganicligandstogiverisetoasmallhydrophobicchannelofthedimensions4.2Å×4.8Åthatextendsthroughtheentirestructureparalleltothesheets.ThedistancebetweentheparallelZnPOsheetsin4is11.23

Å.

7004InorganicChemistry,Vol.44,No.20,2005