通过有机配体界定的锌的磷酸化合物拓扑结构(晶(4)

NoWelZincPhosphateTopologies

Figure1.(a)Fragmentofthestructureofcompound1showingtheatomlabelingscheme.Thermalellipsoidsaredrawnat50%probability(left)andtheconformationofthe8-ring(right.Zn:pink.P:yellow).(b)Packingdiagramofcompound1withthehydrogenbondsindicatedbydashedlines.(c)Schematicdrawingofthe3Dnetworkin1(Zn:pinkball.P:yellowball).

(2)pounds1and2maybemanuallyseparatedfromthereactionmixturebyrecognitionoftheirdifferentcrystalmorphologies.

Theasymmetricunitofcompound1containstwocrys-tallographicallydistinctzincatomsandthreePatoms.Onezincatom(ZnO2N2)iscoordinatedbytwooxygenatomsfromphosphategroupswithanaverageZn-O-Pbondingangleof128.4°andtwonitrogenatomsfromtheL1units[(Zn-O)av)1.929Åand(Zn-N)av)2.008Å];theotherzincatom(ZnO3N)iscoordinatedbythreeoxygensfromphosphategroupswithanaverageZn-O-Pbondingangleof135.9°andonenitrogenfromL1[(Zn-O)av)1.940Åand(Zn-N))2.010Å].Ofthethreephosphorusatoms,P1andP3maketwoP-O-ZnlinkagesandpossesstwoP-Oterminals,an-OHgroupandanunsaturateddOatom(HPO42-),andP2hasoneP-O-ZnlinkageandthreeP-Oterminals.Thus,P2ispendanttothezincphosphateframe.Thehydrogenatomsbondedtothephosphorusgroupswerelocatedintheresiduale-densitymapandrefinedindepen-

dently.ThethreephosphorusatomshaveP-Odistancesintherangeof1.501(4)-1.576(3)Å[(P1-O)av)1.533Å,(P2-O)av)1.534Å,(P3-O)av)1.537Å].

AnORTEPdiagramof1isshowninFigure1a.Theconnectivityofzinc(ZnO2N2andZnO3N)andphosphorus(HPO42-)tetrahedragivesrisetoisolated8-ringswithtwopendantH2PO4-tetrahedrabondedtozincatomsatdiagonalpositions.Tothebestofourknowledge,compound1representsthelargestisolatedringintheZnPOclassofcompounds.Withineach8-ring,Zn1,Zn1A,P1,andP1Aarecoplanar.TheatomsZn2andZn2Aaredisplacedaboveandbelowtheplaneby2.5407Å,andtheatomsP3andP3Alie0.9649Åaboveandbelowtheplane.Additionally,thefourzincatomsarecoplanarandthefourphosphorusatomsarecoplanar.Withinthe8-ring,theZn1-P3-Zn2Aangleis166.9°.Thus,the8-ringadoptsachairconformation,alsoshowninFigure1a.The8-ringsareslightlyskewed,asseenfromtheP-PandZn-Zndistances:P1-P1A)6.789Å;P2-P2A)5.234Å;Zn1-Zn1A)8.559Å;Zn2-Zn2A)7.651Å.The8-ringisstabilizedby

hydrogen

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