通过有机配体界定的锌的磷酸化合物拓扑结构(晶(5)

FanandHanson

Figure2.(a)Asymmetricunitofthestructureofcompound2showingtheatomlabelingscheme.Thermalellipsoidsaredrawnat50%probability.(b)Schematicdrawingofthe4.8-chainin2.(c)Packingdiagramand(d)schematicdrawingofcompound2(Zn:pinkball.P:yellowball).TheconnectionbetweenZnO2N2vertexesisindicatedbyblacklines,andtheconnectionbetweenZnO3Nvertexes,bybluelines.

bondingbetweenintraringphosphategroups;theO10A-O3Adistanceis2.571Å,andtheO10A-H3A-O3Aangleis174.9°.

Apackingdiagramof1isshowninFigure1b.Each8-ringisconnectedintoa3Dhybridframeworkbythreeligands;afourthprotonatedligandactsasatemplateandfillstheinterstitialspaceoftheframework.AschematicversionofthepackingdiagramisgiveninFigure1c,inwhichthe8-ringsareshownwithdirectconnectionsbetweenzincandphosphorusandtheframeworkligandsareshownaslines.Ifeachphosphorusatomandzincatomisconsideredasanode,thenazigzaghybridsheetstructurethatcontainsalternating8-and12-ringsofTatomscanbedescribed.TheTatoms,however,arenotequivalent,eachphosphorusatominthesheetisbiconnected,Zn1istetraconnectedinthesheet,andZn2isbiconnectedinthesheet(withoneadditionalconnectiontoasheetaboveorbelow).ThesheetsarestackedinanAAAfashion.

The8-ringstoichiometryof[Zn4(HPO4)4(H2PO4)2]2-hasanetnegativechargethatisbalancedbytheprotonationoftheextraframeworkligand.20TheextraframeworkligandL1islocatedinthepseudo12-ringchannelandactsasastructure-directingagent,throughN-H OhydrogenbondinteractionswiththeH2PO4-groups[(N7 O6))2.675(6)Å,and(N7-H7B-O6))160°].Thus,L1playsanunusualdualrolein1,asbothligandandtemplate,tostabilizethe3Dstructure.Suchadualrolehasrarelybeenreported.6gTheasymmetricunitofcompound2containstwocrys-tallographicallydistinctzincatomsandtwophosphorusatoms,asshowninFigure2a.Onezincatomistetrahedrallycoordinatedbytwooxygenatomsfromphosphategroups[(Zn-O-P)av)123.6°]andtwonitrogenatomsfromthe

(19)Harrison,W.T.A.;Nenoff,T.M.;Gier,T.E.;Stucky,G.D.J.Solid

StateChem.1994,113,168.

(20)Duetothelowe-densityinchannelsofthisstructure,thehydrogen

atomattachedtothenitrogenatomisadded

geometrically.

7002InorganicChemistry,Vol.44,No.20,2005