通过有机配体界定的锌的磷酸化合物拓扑结构(晶体)

NovelZincPhosphateTopologiesDefinedbyOrganicLigands

JianFanandBrianE.Hanson*

DepartmentofChemistry,VirginiaPolytechnicInstituteandStateUniVersity,Blacksburg,Virginia24061

ReceivedMarch1,2005

Sixnewzincphosphates[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)havebeensynthesizedundermildhydrothermalconditionsinthepresenceof1,4-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),respectively,pound2,alsoformedfromL1,pound3,preparedfromL2,possessesanunusualone-dimensionalframework,whichiscomposedofvertex-sharing4-ringsandtriplefused4-rings.Theinorganicportionsof4,5,and6eachadoptalayerstructure.Thesheetsin4and5havea4.82topology,andin6,a63topologyisobserved.Thezincatomsincompounds1 6arealltetrahedrallycoordinatedbyacombinationofphosphategroupsandorganicligands.Potentialrelationshipsbetweentheinorganicmotifsreportedinthepresentstudyareidentified.Theseareindicativeofapossiblepatternofself-assemblyofzincandphosphorustetrahedraandindicativeoftheroleoftheorganicligandsintheformationofhybridstructures.

Introduction

Frameworkzincmaterialsincludingzincphosphatesareofconsiderableinterestduetotheirwideapplicationintheareasofseparation,catalysis,andabsorption.1Thesynthesisofzincphosphateswithzero-,one-,two-,andthree-dimensional(3D)structureshasbeensuccessfullyachievedduringthepastdecade.2,3Twocommonlyobservedfeatures

*Towhomcorrespondenceshouldbeaddressed.E-mail:hanson@vt.edu.

(1)(a)Rao,C.N.R.;Natarajan,S.;Choudhury,A.;Neeraj,S.;Ayi,A.

A.Acc.Chem.Res.2001,34,80.(b)Murugavel.R.;Walawalkar,D.M.;Roesky,H.W.;Rao,C.N.R.Acc.Chem.Res.2004,37,409.(c)Cheetham,A.K.;Fe´rey.G.;Loiseau,T.Angew.Chem.,Int.Ed.1999,38,3268.(d)Pan,J.X.;Zheng,S.T.;Yang,G.Y.Cryst.GrowthDes.2005,5,231.(e)Wang,Y.;Yu,J.;Guo,M.;Xu,R.Angew.Chem.,Int.Ed.2003,42,4089.

(2)(a)Jensen,T.R.;Gerentes,N.;Jepsen,J.;Hazell,R.G.;Jakobsen,

H.J.Inorg.Chem.2005,44,658.(b)Rao,C.N.R.;Natarajan,S.;Neeraj,S.J.Am.Chem.Soc.2000,122,2810.(c)Neeraj,S;Natarajan,S.;Rao,C.N.R.J.SolidStateChem.2000,150,417.(d)Harrison,W.T.A.;Hanooman,L.J.SolidStateChem.1997,131,363.(e)Yang,G.-Y.;Sevov.S.C.J.Am.Chem.Soc.1999,121,8389.(f)Norquist,A.J.;O’Hare,D.J.Am.Chem.Soc.2004,126,6673.(3)(a)Liu,W.;Liu,Y.;Shi,Z.;Pang,W.J.Mater.Chem.2000,10,

1451.(b)Song,Y.;Yu,J.;Li,Y.;Zhang,M.;Xu,R.Eur.J.Inorg.Chem.2004,3718.(c)Choudhury,A.;Neeraj,S.;Natarajan,S.;Rao,C.N.R.J.Mater.Chem.2001,11,1537.(d)Natarajan,S.;Wullen,L.V.;Klein,W.;Jansen,M.Inorg.Chem.2003,42,6265.

oftheobservedstructuresarethattheinorganicframeworksareoftenanionicandaprotonatedorganicamine,usedasatemplatingagent,directsthestructureformationbyfillingthevoidspaceandinteractingwiththeframeworkwithmultipointN-H Of(f)framework)hydrogenbonds.4Forexample,Raoandco-workersdevelopedasimpleuniversalrouteinwhichthereactionofaminephosphateandmetalionsyieldsahierarchyoftemplatedstructures.2bFurther,itisobservedthatphosphorusgroupsmodifiedbyorganicunitsareveryeffectiveintheconstructionofhybridmaterials.5Untilrecently,hybridzincphosphates/phosphitesthatcontaindirectZn-Nbondshavebeenrarelyreported.6Inthesecases,theorganicgroupscoordinatetothemetalionsoftheframeworkandactasstructure-buildingunits.Harrison,forexample,reportedR-and -ZnHPO3 N4C2H4asthefirstorganicallymodifiedzincphosphites.6aTheligands2,2′-dipyridine7andimidazoles6c,8havealsobeenreportedto

(4)Gordon,L.E.;Harrison,W.T.A.Inorg.Chem.2004,43,1808.(5)Shi,X.;Zhu,G.;Qiu,S.;Huang,K.;Yu,J.;Xu,R.Angew.Chem.,

Int.Ed.2004,43,6482.(b)Cao,D.K.;Gao,S.;Zheng.L.M.J.SolidStateChem.2004,177,2311.(c)Go´mez-Alca´ntara,M.M.;Cabeza,A.;Mart ´nez-Lara,M.;Aranda,M.A.G.;Suau,R.;Bhuvanesh,N.;Clearfield,A.Inorg.Chem.2004,43,5283.(d)Lei,C.;Mao,J.G.;Sun,Y.Q.J.SolidStateChem.2004,177,2449;(e)Clearfield,A.Prog.Inorg.Chem.1998,47,375andreferencestherein.

6998InorganicChemistry,Vol.44,No.20,2005

10.1021/ic050314tCCC:$30.25©2005AmericanChemicalSociety

PublishedonWeb09/10/2005

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.

InorganicChemistry,Vol.44,No.20,2005

6999

wt%,230.6mg,2.0mmol),1,4-bis(N-benzimidazolyl)butane(435.0mg,1.5mmol),andwater(6mL)for10daysat130°Cyieldscolorlessmicrocrystallineproducts1and2.

[Zn3(HPO4)3(H2PO4)(C22H22N8)0.5(C22H24N8)0.5](3).Hydro-thermaltreatmentofzincacetatedihydrate(219.5mg,1.0mmol),phosphoricacid(85wt%,230.6mg,2.0mmol),1,2,4,5-tetrakis-(imidazol-1-ylmethyl)benzene(169.0mg,0.5mmol),andwater(6mL)for10daysat130°Cyieldsseveralcrystallineproducts,compound3,andoneadditionalcompound,7,thatgivescrystalsofpoorquality.16

[Zn2(HPO4)2(C18H16N4)](4).Hydrothermaltreatmentofzincacetatedihydrate(65.8mg,0.3mmol),potassiumdihydrogenphos-phate(81.6mg,0.6mmol),1,4-bis(imidazol-1-ylmethyl)naphthalene(86.4mg,0.3mmol),andwater(6mL)for10daysat130°Cyieldsaplatecrystallineproduct.Yield:84%onthebasisofzincsource.Fouriertransforminfrared(FT-IR)spectroscopy(cm-1):3091(w),1526(m),1453(m),1389(m),1281(w),1253(w),1203(m),1118(m),1092(s),1045(m),1023(s),974(m),915(s),847(m),807(m),773(m),741(s).Thermogravimetricanalysis(TGA):<0.2%weightlossto150°C.Anal.CalcdforC9H9N2O4-PZn:C,35.38;H,2.97;N,9.17.Found:C,35.31;H,3.19;N,9.15.

[Zn(HPO4)(C18H14N2)](5).Hydrothermaltreatmentofzincacetatedihydrate(219.5mg,1.0mmol),phosphoricacid(85wt%,115.3mg,1.0mmol),9-(imidazol-1-ylmethyl)anthracene(258.0mg,1.0mmol),andwater(6mL)for10daysat130°Cyieldsaplatecrystallineproduct.Yield:65%onthebasisofzincsource.FT-IR(cm-1):3100(w),1623(w),1576(w),1525(m),1447(m),1402(m),1335(m),1256(m),1205(m),1181(m),1118(m),1096-(m),1046(s),1015(s),949(m),903(s),851(m),799(m),745(m),722(s).Fluorescencespectrum(nm,excitationat350nm):421,446inaratioof1.2/1,475(shoulder).TGA:<0.4%weightlossto150°C.Anal.CalcdforC18H15N2O4PZn:C,51.52;H,3.60.;N,6.68.Found:C,51.25;H,3.93;N,6.65.

[Zn2(HPO4)2(C12H10N4)](6).Hydrothermaltreatmentofzincacetatedihydrate(219.5mg,1.0mmol),phosphoricacid(85wt%,230.6mg,2.0mmol),1,4-bis(1-imidazolyl)benzene(315.0mg,1.5mmol),andwater(6mL)for10daysat130°Cyieldsaneedlecrystallineproduct.Yield:77%onthebasisofzincsource.FT-IR(cm-1):3137(w),1646(m),1541(m),1533(m),1317(m),1204(m),1165(m),1130(m),1110(m),1025(s),960(m),948(m),911(s),846(m),835(m),799(m),770(m).TGA:140°Cdec.Anal.CalcdforC6H6N2O4PZn:C,27.04;H,2.27.;N,10.51.Found:C,27.04;H,2.64;N,10.41.

CrystallographicAnalyses.Lowtemperature(100K)single-crystalX-raydiffractionmeasurementsforcomplexes1-6werecollectedonanOxfordDiffractionXcalibur2diffractometerequippedwiththeEnhanceX-raysourceandaSapphire2CCDdetector.Thedatacollectionroutine,unitcellrefinement,anddataprocessingwerecarriedoutwiththeprogramCrysAlis.17ThestructurewassolvedbydirectmethodsusingSHELXS-97andrefinedbyfull-matrixleast-squaresanalysis.18Thefinalrefinementsinvolvedananisotropicmodelforallnon-hydrogenatoms.Hy-drogenatomswereeitherlocatedfromtheresiduale-densitymapandrefinedindependentlyorlocatedbyaridingmodel.Thehydrogenatomsbondedtotheoxygenatomoflatticewater

(16)Crystaldatafor7:triclinic,spacegroupP1h,a)10.0683Å,b)

14.9733Å,c)15.6267Å,R)88.702°, )83.786°,γ)89.130°,V)2341.18Å3,andZ)2.

(17)CrysAlis,version1.171;OxfordDiffraction:Wroclaw,Poland,2004.(18)(a)Sheldrick,G.M.SHELXS97:ProgramforCrystalStructure

Determination;UniversityofGo¨ttingen:Germany,1997.(b)Sheld-rick,G.M.SHELXL97:ProgramforCrystalStructuralRefinement;UniversityofGo¨ttingen:Germany,1997.

7000InorganicChemistry,Vol.44,No.20,2005

FanandHanson

Table2.SelectedBondDistances(Å)andAngles(deg)for1-6a

1

Zn1-O2

1.921(3)Zn1-O121.937(3)Zn1-N12.006(4)Zn1-N52.010(4)Zn2-O81.912(3)Zn2-O41.947(3)Zn2-O11#11.962(3)Zn2-N3

2.010(4)O2-Zn1-O12120.34(14)O2-Zn1-N1107.07(15)O12-Zn1-N1112.37(15)O2-Zn1-N5102.38(14)O12-Zn1-N5107.02(14)N1-Zn1-N5106.41(16)O8-Zn2-O4109.96(14)O8-Zn2-O11#1103.34(14)O4-Zn2-O11#1118.43(13)O8-Zn2-N3110.43(15)O4-Zn2-N398.67(15)

O11#1-Zn2-N3116.09(14)2

Zn1-O21.933(2)Zn1-O81.955(2)Zn1-N31.992(3)Zn1-N12.007(3)Zn2-O4#21.911(2)Zn2-O5#31.928(2)Zn2-O3

1.928(2)Zn2-N5

2.029(3)O2-Zn1-O8108.79(9)O2-Zn1-N3123.31(10)O8-Zn1-N398.68(10)O2-Zn1-N1103.72(10)O8-Zn1-N1110.86(10)N3-Zn1-N1111.32(11)O4#2-Zn2-O5#3122.54(10)O4#2-Zn2-O3116.66(10)O5#3-Zn2-O3104.02(10)O4#2-Zn2-N5102.52(10)O5#3-Zn2-N5104.46(10)

O3-Zn2-N5104.64(10)3

Zn1-O31.916(3)Zn1-O111.954(3)Zn1-O71.968(3)Zn1-N3#42.011(4)Zn2-O81.891(4)Zn2-O41.945(3)Zn2-O61.968(3)Zn2-N11.991(4)Zn3-O121.934(3)Zn3-O91.938(3)Zn3-O14

1.951(3)Zn3-N5

2.005(4)O3-Zn1-O11110.71(13)O3-Zn1-O7114.16(13)O11-Zn1-O7103.35(13)O3-Zn1-N3#4117.10(14)O11-Zn1-N3#497.17(14)O7-Zn1-N3#4112.08(14)O8-Zn2-O4105.66(16)O8-Zn2-O6124.69(15)O4-Zn2-O699.25(13)O8-Zn2-N1106.-05(16)O4-Zn2-N1108.64(15)O6-Zn2-N1111.40(14)O12-Zn3-O9112.40(14)O12-Zn3-O14111.80(13)O9-Zn3-O14110.89(13)O12-Zn3-N597.78(15)O9-Zn3-N5108.72(14)

O14-Zn3-N5114.66(15)4

Zn1-O41.920(3)Zn1-O21.938(3)Zn1-O3

1.956(3)Zn1-N1

1.998(4)O4-Zn1-O2107.13(14)O4-Zn1-O3120.76(14)O2-Zn1-O3110.31(14)O4-Zn1-N1107.31(16)O2-Zn1-N1111.67(15)

O3-Zn1-N199.41(16)5

Zn1-O11.919(3)Zn1-O21.957(4)Zn1-O3

1.964(3)Zn1-N1

2.008(5)O1-Zn1-O2108.26(15)O1-Zn1-O3109.81(15)O2-Zn1-O3102.94(15)O1-Zn1-N1118.12(17)O2-Zn1-N1108.15(17)

O3-Zn1-N1108.49(17)6

Zn1-O31.9283(14)Zn1-O11.946(3)Zn1-O4

1.9530(14)Zn1-N1

2.0028(14)O3-Zn1-O1111.04(10)O3-Zn1-O4108.16(7)O1-Zn1-O4116.61(10)O3-Zn1-N1108.27(7)O1-Zn1-N1

109.06(10)

O4-Zn1-N1

103.19(7)

a

Symmetrytransformationsusedtogenerateequivalentatoms:(#1)-x+1,-y,-z+2;(#2)-x,-y+2,-z;(#3)-x+1,-y+2,-z;(#4)x,y,z+1.

moleculesin1and2werenotlocated.Thedisorderedcarbonatoms,C30(sof:0.72and0.28)in1andC27(sof:0.63and0.37)in2,arelocatedwiththesiteoccupancyfactor(sof)givenintheparentheses.Thecrystalparameters,datacollection,andrefinementresultsforcompounds1-6aresummarizedinTable1.SelectedbondlengthsandanglesarelistedinTable2.FurtherdetailsareprovidedintheSupportingInformation.

Results

CrystalStructures[C18H20N4][Zn4(HPO4)4(H2PO4)2-(C18H18N4)3] 2H2O(1)and[Zn4(HPO4)4(C18H18N4)3] 4H2O

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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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.

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L1ligands[(Zn-O)av)1.944Åand(Zn-N)av)1.999Å];theotherzinciscoordinatedbythreeoxygensfromphosphategroups[(Zn-O-P)av)135.4°]andonenitrogenfromL1[(Zn-O)av)1.922Åand(Zn-N))2.029Å].ThetwophosphorusatomsareconnectedsuchthatP1islinkedtoZnbythreeP-O-ZnlinkagesandP2isconnectedtozincbytwoP-O-Znlinkages.ThelongestP-Obondlengthforthetwophosphorusgroupsis1.570(2)Åand1.589(2)Å,respectively,correspondingtothe-OHgroup.21Thus,eachphosphorusgroupisaHPO42-anion.Toconfirmtheassignment,thehydrogenatomsattachedtothephos-phorusgrouparelocatedintheresiduale-densitymapandrefinedindependently.Theresultingstoichiometry,Zn2-(HPO4)2,givesaneutralframework.

Theinorganicmotifin2consistsofaone-dimensional(1D)polymericzinc-oxygen-phosphatechainconstructedfromedge-sharing4-ringsand8-rings,asillustratedinFigure2b.Thestrictlyalternating4-ringand8-ringpatternappearsfrequentlyinzincphosphates/phosphites,especiallyin4.82-sheets.22However,isolated4.8-chainshavenotbeenprevi-ouslyreported.The4.8-chainscanformeitherbyjoining8-ringsinsuchawaytocreatethe4-ringorbyformingasimpleladderandcleavingtwooutofeveryfourrungsintheladder.

ThetwozincatomswithaZnO3Ncoordinationsetarecontainedwithinthe8-ringsand4-rings;thetwozincatomsthathaveaZnO2N2coordinationsetareonlyfoundinthe8-rings.In2,thechainstructuresareparallelandpropagatealongthe[100]direction,asshowninFigure2c.InFigure2d,each4.8-chainisshownconnectedto6neighboringchainsviaL1ligandstoforma3Dstructure.

CrystalStructureof[Zn3(HPO4)3(H2PO4)(C22H22N8)0.5-(C22H24N8)0.5](3)pound7givescrystalsofinsufficientqualityforadeterminationofthecompletestructure,whichappearstobea3Dhybridframework,andtherefinementisnotofahighenoughqualityforpublication.Acompletestructureofthecompounddesignatedas3wasdetermined.Theasymmetricunitof3containsthreecrystallographicallydistinctZnatomsandfourPatoms,asshowninFigure3a.EachzincatomistetrahedrallycoordinatedbythreephosphateoxygenatomsandoneimidazolenitrogenfromL1:(Zn1-O)av)1.946Å,(O-Zn1-O)av)109.4°,(O-Zn1-N)av)108.8°;(Zn2-O)av)1.935Å,(O-Zn2-O)av)109.9°,(O-Zn2-N)av)108.7°;(Zn3-O)av)1.941Å,(O-Zn3-O)av)111.7°,(O-Zn3-N)av)107.0°.Ofthefourphosphategroups,P1coordinatestotwozincatoms,P2andP3coordinatetothreezincatoms,andP4coordinatestoonezincatom.TheP-Odistances[(P1-O1))1.590(3),(P2-O5))1.564(3),(P3-O10))1.563(3),(P4-O13))1.576(3),and(P4-O16))

(21)Brown,I.D.;Aldermatt,D.ActaCrystallogr.1984,B41,244.

(22)(a)Gordon,L.E.;Harrison,W.T.A.ActaCrystallogr.2004,C60,

m637.(b)Harrison,W.T.A.Int.J.Inorg.Mater.2001,3,179.(c)Ayi,A.A.;Choudhury,A.;Natarajan,S.;Rao,C.N.R.J.Mater.Chem.2000,10,2606.(d)Zhang,D.;Shi,Z.;Dong,W.;Fu,W.;Wang,L.;Li,G.;Feng,S.J.SolidStateChem.2004,177,

343.

Figure3.(a)Crystalstructureofcompound3withatomlabelingscheme.Thermalellipsoidsaredrawnat50%probability.(b)Schematicdrawingofthe1Dchainin3.(c)2Dstructureofcompound3.

1.590(3)Å]indicatethattheterminaloxygens(O1,O5,O10,O13,andO16)are-OHgroups.21

AsshowninFigure3b,theinorganicstructureof3consistsofaone-dimensionalchainconstructedfromalternating4-ringsandtriplefused4-ringsthatareconnectedthroughonevertex.The4-ringsarecomposedofvertex-sharingZn3andP3tetrahedra,andthetetrahedralcoordinationenviron-mentofZn3iscompletedbytwoP3bridginggroups,anL2ligand(N5),andapendantP4group.Thetriplefused4-ringiscomposedofthreeedge-sharing4-ringsofZnO3N(Zn1andZn2)andHPO4(P1andP2)tetrahedra.The4-ringisawell-knownsecondarybuildingunit,andthetriplefused4-ringhasrecentlybeensuggestedasatertiarybuildingunit.10Thechainstructurecomposedofthestrictlyalternating4-ringandtriplefused4-ringisnewandmaybedescribedasarisingfromtheself-assemblyoftriple4-ringsand4-rings.Alternatively,itmaybeconsideredtobeafrustratedladderstructureinwhichthependantphosphategrouppreventstheformationoftheladdermotif.

Compound3containstwotypesofL2ligands:onecoordinatestofourzincatomsasatetradentatebridgingligand,andtheothercoordinatestotwozincatomsasabidentatebridgingligand,asseeninthepartialpackingdiagraminFigure3c.Thefragment,[Zn3(HPO4)3(H2PO4)]2,hasanetframeworkchargeof-2whichisbalancedbythediprotonationofthetwounligatedimidazolegroupsofthebidentatebridgingL2ligand.Toconfirmtheassignment,thehydrogenatomsattachedtothefreearms(N7andN7A)

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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.

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Figure5.(a)Asymmetricunitofthestructureofcompound5showingtheatomlabelingscheme.Thermalellipsoidsaredrawnat50%probability.(b)Packingdiagramofcompound5.

Theasymmetricunitin5containsonecrystallographicallyindependentzincatom,aphosphategroup,andanL4ligand,asillustratedinFigure5a.Thezincphosphateportionofthestructureisagaina4.82-sheetwithaherringbonepatternof8-ringssimilartothatobservedincompound4.In5,thesheetisdecoratedonbothsidesbythemonodentateL4ligand.Thus,thesheetsareneutralandheldtogetheronlybyvanderWaalsforcestoforma3Dstructure.ApackingdiagramisshowninFigure5b.Thenearestapproachbetweenanthracenehydrogenatomsfromadjacentsheetsis2.65Å,butthereisnoπoverlap.TheshortestH-Xcontactbetweenanthraceneringsassociatedwithasinglesheetis3.06Å(X

referstothecentroidofthebenzenering)withaC-H-Xangleof130.4°.Thisindicatesweakinteractionswithineachsheet.Thepackingofanthracenegroupsononesideofazincphosphatesheetmimicstheherringbonepatternof8-ringsinthe4.82-net.Thatis,thereisoneanthraceneringper8-ringoneachsideofthezincphosphateplaneandeachfillsthespaceabovean8-ringwiththelongaxisofanthraceneprojectedontothelongaxisofthe8-ring.Thezincatomswithinasheetarecoplanar,andthedistancebetweenthelayersis19.72Å.

StructureofCompound[Zn2(HPO4)2(C12H10N4)](6).Compound6isformedfromzincphosphateandtherigidbidentateligandL5.Theasymmetricunitofcompound6containsonecrystallographicallyindependentzincatom,aphosphategroup,andhalfofanL5ligand,asshowninFigure6a.EachzincatomistetrahedrallycoordinatedbythreephosphateoxygenatomsandanitrogenfromL5[(Zn1-O)av)1.942Å,(O-Zn1-O)av)111.9°,and(O-Zn1-N)av)106.8°].EachphosphategroupcoordinatestothreezincatomsthroughP-O-Znlinkages[(P-O-Zn)av)121.8°].

AsshowninFigure6b,theinorganiclayerin6iscomposedsolelyof6-ringstogivea63topology.The6-ringinzincphosphatesisknown,23specificallyinthesodalitestructure;however,theplanar6-ringpattern,asin6,hasnotbeenobservedpreviouslyforzincphosphates.Recently,Harrisonreportedathree-dimensionalzincphosphitestruc-ture,(C6N2H8)0.5 ZnHPO3,inwhichaninorganicsheetwiththe63topologyispillaredby1,4-diaminobenzene.6bIn6,theparallelzincphosphatesheetsarelinkedbyL5ligands.Theligandsonoppositesidesofthesheetsleansignificantlyfromtheperpendicular;themajoraxisoftheligandshasanangleofabout50°withrespecttothesheet.Thus,thepillarsleansignificantlytocompresstheinterlayerspacingto8.3Åinthe3Dstructure.ThepackingofthesheetsandtheL5pillarsisshowninFigure6c.Discussion

Ofthefiveligandsusedtopreparesixnewzincphosphatephasesinthisstudy,thetwowiththegreatestflexibility,L1andL2,pounds1and2formwithL1;compound3andthestructurallyuncharac-terizedphase7formwithL2.TheobservationofmixedproductswiththeseligandsisattributedtotheflexibilityandmultifunctionalityofL1andL2.

Compounds1and3containbothHPO42-andH2PO4-,whilecompounds2,4,5,and6containonlyHPO42-.Further,thestoichiometryof1and3requiresextraframeworkcationstobalancethenetanionicchargeoftheframeworks.DiprotonatedL1servestheroleofextraframeworkcationin1,andin3,twoimidazolegroupsofthetetradentateligandL2areprotonated.DihydrogenphosphateandsubstitutedimidazoleshavesimilarpKa’s.Thus,thesesystemsthat

(23)(a)Kongshaug,K.O.;Fjellvag,H.;Lillerud,K.P.SolidStateSci.

2000,2,569.(b)Rodgers,J.A.;Harrison,W.T.A.J.Mater.Chem.,2000,10,2853.(c)Feng,P.;Bu,X.;Stucky,G.D.Angew.Chem.,Int.Ed.Engl.1995,34,1745.(d)Jensen,T.R.;Norby,P.;Stein,P.C.;Bell,A.M.T.J.SolidStateChem.1995,117,

39.

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Figure6.(a)Crystalstructureofcompound6withatomlabelingscheme.Thermalellipsoidsaredrawnat50%probability.(b)Polyhedralrepresentationofthe2Dsheetin6(Zn:blue.P:yellow).(c)Packingdiagramofcompound6.

containbothphosphoricacidandimidazolehaveflexibilityinthelocationofprotonsrequiredforchargebalance.Thoughtheexactmechanismintheaufbauprocessisfarfrombeingunderstood,itiscertainthattheligandandsolutionpHplayimportantroles.

Intheligandmodifiedzincphosphatestructuresreportedhereandintheliterature,thereappearstobeacompetitionbetweennitrogendonoratomsandphosphateoxygenforzinccoordinationsites.Thus,onecanenvisionalternativestruc-turesformanyligand/metalcombinations.Forexampleanalternativefor3couldhavebeenformedbytheadditionalcoordinationofthezincatomintheterminalringsofthetriple4-ringwithconcomitantdeprotonationoftheL2.ThiscouldleadtostructureAasillustratedinScheme2.Suchastructureremainshypothetical.

Theincorporationofmultifunctionalligandsintozincphosphateframeworksisapowerfulrouteforthesynthesisofinorganic/organichybridmaterials.Imidazoleandbenz-imidazolegroupsareeffectivecompetitorswithphosphateionsforzinccoordinationsites.Thisleadstothecleavageofzincphosphatephasesintofragmentsthatincluderings,chains,andsheets.Themannerinwhichtheinorganicfragmentscanbeputtogethertoformhybridmaterialsis

Scheme2.PossibleTransformationoftheChainObservedin3ToGiveaHypotheticalChainof4-RingsLinkedbyZincAtoms(Zn:Pink.P:Yellow)

a

a

Pendantphosphategroupson4-ringsareomittedforclarity.

dictatedbytheligandandthecoordinationrequirementsofthefragments.Fromthestructuresdescribedabove,itappearsthattheinorganicpiecesin1,2,4,and5arecloselyrelatedasillustratedinScheme3.Startingfromthecommonlyobserved4-ring,two4-ringsmaylinktogethertogenerateatriplefused4-ringandtriple4-ringsmaycondensefurthertogiveladdersorstairsteps.Alternatively,thetriple4-ringmayopenuptogeneratesingle8-ringssuchasthoseobservedin1.Thelinkingof8-ringsalongone

direction

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Scheme3.SchemefortheFormationofCompounds1-6from4-Rings

a

a

Thenewconnectionsarerepresentedbyshortbars(Zn:pink.P:yellow).

generatesthe4.8-chainasobservedin2.When8-ringsareconnectedintwodirections,then,4.82-sheetsareobtainedasobservedin4and5.Theladderstructurecanalsobeconsideredasapossibleintermediateintheformationofthe4.8-chain.Forexample,iftwoofeveryfourrungsofa4-ringladderarecleaved,a4.8-chainresults.Similarly,the63-sheetcanbeobtainedviathecleavageandconnectionpatternshowninScheme3.Theladderstructuremayalsobecleavedtogeneratethealternatingtriple4-ring/4-ringpatternof3.Alternatively,theinorganicmotifin3canbeconstructed

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bythecombinationoftwobuildingblocks,the4-ringandthetriplefused4-ring.Conclusion

Inthispaper,sixtailoredinorganiczincphosphatemotifsareobservedwhentheligandsL1-L5modifythezincions.Atthepresenttime,thesize,Zn/Pratio,andtheframeworkofthezincphosphatephasescannotbecontrolledasdesired.However,potentiallyporousmaterialscanbeexpectedwhiletheZn-Pphaseislinkedbyrigidligands.Wearecurrentlyinvestigatingtheuseofrigidligandsintheconstructionofsuchporousmaterials.

Acknowledgment.WethankR.J.ReynoldsforsupportofthisworkthroughaMcNairpostdoctoralfellowshiptoJ.F.WethanktheNSF(GrantCHE-0131128)forfundingthepurchaseoftheOxfordDiffractionXcalibur2singlecrystaldiffractometer.WethankMs.LiangmingHufortheTGA.WethankMarkElvingtonfortheemissionspectra.

SupportingInformationAvailable:FigureS1,showingthepackingdiagramof3,andX-raycrystallographicfilesinCIFformat.ThismaterialisavailablefreeofchargeviatheInternetat.

IC050314T

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