通过有机配体界定的锌的磷酸化合物拓扑结构(晶(3)

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

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