通过有机配体界定的锌的磷酸化合物拓扑结构(晶(2)

NoWelZincPhosphateTopologies

Table1.CrystalDataandStructureRefinementParametersfor1-6structureparameterempiricalformulafwT(K)

spacegroupa(Å)b(Å)c(Å)R(deg) (deg)γ(deg)V(Å3)Z

Dcalc(gcm-3)µ(mm-1)R1a[I>2σ(I)]wR2b[I>2σ(I)]

a

1

C36H43N8O13P3Zn21019.43100P1h

10.3187(10)13.6651(14)16.1419(16)102.047(8)108.580(9)99.147(8)2046.6(4)21.6541.3650.06130.1452

2

C27H33N6O10P2Zn2794.27100P1h

9.0382(9)13.6616(10)13.7094(9)99.997(6)101.158(7)108.140(8)1527.8(2)21.7271.7430.04750.1263

3

C22H28N8O16P4Zn3980.51100P21/c

14.9410(10)14.6445(7)15.8209(11)109.503(6)3263.1(4)41.9962.4720.03880.1030

4C9H9N2O4PZn305.52100Pnma8.7620(7)28.368(3)8.7638(7)

5

C18H15N2O4PZn419.66100P21/c19.715(3)8.4865(10)9.9938(10)95.485(9)

6C6H6N2O4PZn266.47100P21/n5.2956(6)20.243(2)7.5816(9)100.041(10)800.29(16)42.2123.2550.03700.0863

2178.3(3)81.8632.4050.06080.11171664.4(3)41.6751.6000.06890.1536

R1)||Fo|-|Fc||/|Fo|.bwR2){|[w(Fo2-Fc2)2]|/[w(Fo2)2]}1/2,wherew)1/[σ2(Fo)2+(aP)2+bP]andP)[(Fo)2+2(Fc)2]/3.

Scheme1.LigandsL1-

L5

decoratemetalionsinthesynthesisofhybridnetworks.Recently,wehaveshownthatbisimidazoleligandsareveryeffectiveinorganizingzincphosphatesandzincphosphitesintonewstructures.9,10Forexample,1,4-bis(imidazol-1-ylmethyl)benzeneknitsthewell-knownzincphosphateladderstructuretogethertoformahybridsheet,9and1,3-bis-(imidazol-1-ylmethyl)benzenetieszincphosphitestairstepsintoa3Dnetwork.10

Despitethediscoveryofnumerouscompoundswithnovelstructures,theunderstandingoftheformationofzincphosphates/phosphitescontinuestobepoor.3dHere,weuseaseriesofmultifunctionalorganicligandstomodifytheaggregationofthezincandphosphorustetrahedra,toobtaininformationonhowthetailoredinorganicpiecescanbeconnected.Sixnewzincphosphatesarereported,[C18H20N4]-[Zn4(HPO4)4(H2PO4)2(C18H18N4)3] 2H2O(1),[Zn4(HPO4)4-(C18H18N4)3] 4H2O(2),[Zn3(HPO4)3(H2PO4)(C22H22N8)0.5-(C22H24N8)0.5](3),[Zn2(HPO4)2(C18H16N4)](4),[Zn(HPO4)-(C18H14N2)](5),and[Zn2(HPO4)2(C12H10N4)](6).ThezincatomsaredecoratedbytheligandsshowninScheme1:1,4-bis(N-benzimidazolyl)butane(L1),1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene(L2),1,4-bis(imidazol-1-ylmethyl)-naphthalene(L3),9-(imidazol-1-ylmethyl)anthracene(L4),and1,4-bis(1-imidazolyl)benzene(L5).

(6)(a)Harrison,W.T.A.;Phillips,M.L.F.;Stanchfield,J.;Nenoff,T.

M.Inorg.Chem.2001,40,895.(b)Kirkpatrick,A.;Harrison,W.T.A.SolidStateSci.2004,6,593(c)Cui,A.;Yao,Y.Chem.Lett.2001,1148.(d)Neeraj,S.;Natarajan,S.;Rao,C.N.R.NewJ.Chem.1999,303.(e)Rodgers,J.A.;Harrison,mun.2000,2385.(f)Ayi,A.A.;Choudhury,A.;Natarajan,S.;Rao,C.N.R.J.Mater.Chem.2001,11,1181.(g)Choudhury,A.;Natarajan,S.;Rao,C.N.R.Inorg.Chem.2000,39,4295.(h)Liang,J.;Wang,Y.;Yu,J.;Li,Y.;Xu,mun.,2003,882.

(7)(a)Hagrman,P.J.;Hagrman,D.;Zubieta,J.Angew.Chem.,Int.Ed.

1999,38,2638.(b)Lin,Z.;Zhang,J.;Yang,G.Inorg.Chem.2004,43,797.(c)Lin,Z.;Zhang,J.;Zheng,S.;Yang,mun.2003,6,1035.(d)Mandal,S.;Pati,S.K.;Green,M.A.;Natarajan,S.Chem.Mater.2005,17,638.

(8)(a)Xing,Y.;Liu,Y.;Shi,Z.;Zhang,P.;Fu,Y.;Cheng,C.;Pang,W.

J.SolidStateChem.2002,163,364.(b)Natarajan,S.;Neeraj,S.;Rao,C.N.R.SolidStateSci.2000,2,87.

(9)Fan,J.;Slebodnick,C.;Angel.R.;Hanson,B.E.Inorg.Chem.2005,

44,552.

(10)Fan,J.;Slebodnick,C.;Troya,D.;Angel,R.;Hanson,B.E.Inorg.

Chem.2005,44,2719.

ExperimentalSection

MaterialsandMeasurements.Allcommerciallyavailablechemicalsareofreagentgradeandusedasreceivedwithoutfurtherpurification.Theligands1,4-bis(N-benzimidazolyl)butane(L1),111,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene(L2),121,4-bis(imi-dazol-1-ylmethyl)naphthalene(L3),139-(imidazol-1-ylmethyl)an-thracene(L4),14and1,4-bis(1-imidazolyl)benzene(L5)15weresynthesizedaccordingtotheliterature.ElementalanalysesofC,H,andNwereperformedbyGalbraithLaboratories,Inc.EmissionspectrawererecordedonaPTIAlphascanfluorimeterwithathermoelectricallycooledR666Sphotomultipliertube.

Allthesynthesesofhybridmaterialsinthispaperwerecarriedoutinheavy-walltubeswithafillfactorof40%.Caution:ThetubesarepotentiallyexplosiVeunderhightemperatureandpressureandshouldbehandledwithcare.ThepHvaluesweremeasuredwithpHpaperbeforeandafterreaction.ThepHofthesystemsisintherangeof5-7anddoesnotappeartochangesignificantlyduringthecourseofthereaction.

[C18H20N4][Zn4(HPO4)4(H2PO4)2(C18H18N4)3] 2H2O(1)and[Zn4(HPO4)4(C18H18N4)3] 4H2O(2).Hydrothermaltreatmentofzincacetatedehydrate(219.5mg,1.0mmol),phosphoricacid(85

(11)Shi,Z.Q.;Thummel,.Chem.1995,60,5935.

(12)Murai,S.;Mikoshiba,S.;Sumino,H.;Hayase,S.J.Photochem.

Photobiol.,A2002,148,33.

(13)Zou,R.;Xu,F.;Li,Q.;Zhang,Z.ActaCrystallogr.2003,E59,o1451.(14)Liu,Q.;Xu,F.;Li,Q.;Zeng,X.;Leng,X.;Chou,Y.;Zhang,Z.

Organometallics2003,22,309.

(15)Cristau,H.;Cellier,P.P.;Spindler,J.;Taillefer,M.Chem.sEur.J.

2004,10,5607.

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