铕(Ⅲ)-镝(Ⅲ)苯并咪唑-5,6-二羧酸配位聚合物的合成和晶体结构

：2012-06-16。：2012-09-15。(No．21071101)。＊。E-mail：[e-mail]髥/髥-5，6-董丽娜马雪查玉娥李夏＊(首都师范大学化学系，北京100048)：{[Ln(Hbmdc)(bmdc)(H2O)3]·3H2O}n(Ln=Eu，1；Dy，2；H2bmdc=-5，6-)，X-。，P21/c。12。H2bmdc2Ln3+：bmdcHbmdc。bmdc2/；Hbmdc1，1。Ln3+63，9。Ln3+bmdc。π-π。12Eu3+Dy3+。：；5，6-；：O614.33+8；O614.342：A：1001-4861(2013)03-0516-07DOI：10.3969/j.issn.1001-4861.2013.00.029SynthesisandCrystalStructureofEu髥/Dy髥CoordinationPolymerswithBenzimidazole-5,6-dicarboxylateAcidDONGLi-NaMAXueCHAYu-ELIXia＊(DepartmentmentofChemistry,CapitalNormalUniversity,Beijing100048,China)Abstract:Thecomplexes{[Ln(Hbidc)(bidc)(H2O)3]·3H2O}n(Ln=Eu1,Dy2;H2bidc=benzimidazole-5,6-dicarboxylicacid)havebeenobtainedbyhydrothermalmethodandcharacterizedbyX-raysingle-crystaldiffraction.Thetwocomplexesbelongtomonoclinicsystem,P21/cspacegroup.Complexes1and2havesimilar1Dchainstructures.Ln3+ionisnine-coordinatedbysixoxygenatomsofcarboxylategroupsandthreeoxygenatomofwatermolecules.Ln3+ionsarelinkedbybmdcligandstoforma1Dhelicalchain.Theright-andleft-handedchainsarefurtherconnectedtoform3Dnetworkviainterchainhydrogenbondsandπ-πstackinginteractions.ThetwocomplexesbehavecharacteristicfluorescenceofEu3+andDy3+ions,respectively.CCDC:883519,1;883518,2.Keywords:rareearthcomplex;benzimidazole-5,6-dicarboxylateacid;crystalstructure0，、、、[1-4]。。，，-，、、、[5-18]，[5-8]。π-π。29320133Vol．29No．3516-522CHINESEJOURNALOFINORGANICCHEMISTRY3：髥/髥-5，6-、。-5，6-，,，[12-18]。,。，，。髥/髥,-5，6-2{[Ln(Hbmdc)(bmdc)(H2O)3]·3H2O}n(Ln=Eu，1；Dy，2；H2bmdc=-5，6-)。、。11.1-5，6-，，，。BrukerSmart1000CCD，296(2)K，MoKα(λ=0.071073nm)。ElementarVarioEL；KBrBrukerEQUINOX-554000~400cm-1。F-4500。BrukerDTG-60AH-，Al2O3，，10℃·min-1，1000℃-。1.21：0.1mmolEu(NO3)3·6H2O、0.15mmol5，6-10mL，25mL，1.0mol·L-1NaOHpH4~5，，170℃3d，。，，40%。C18H21N4O14Eu(669.35)，(%)：C32.30，H3.16，N8.37；(%)：C32.02，H2.96，N8.65。IR(cm-1)：3400br、1425s、1380vs、1269m、1194vs、857m、790s、634m、506w、435w。21，Dy(NO3)3·6H2OEu(NO3)3·6H2O，，36%。C18H21N4O14Dy(679.89)，(%)：C31.80，H3.11，N8.24；(%)：C31.54,H2.98，N8.51。IR(cm-1)：3407br、1429s、1377vs、1261m、1189vs、867m、787s、629m、508w、430w。1.30.30mm×0.30mm×0.27mm(1)0.27mm×0.27mm×0.23mm(2)，BrukerSmart1000CCDX-，MoKα(λ=0.071073nm)。[19]，。F2[20]。，。1，2。CCDC：883519，1；883518，2。112Table1Crystaldataandstructurerefinementforthecomplexes1and2Complex12EmpiricalformulaC18H21N4O14EuC18H21N4O14DyFormulaweight669.35679.89CrystalsystemMonoclinicMonoclinicSpacegroupP21/cP21/ca/nm1.10978(17)1.10652(19)b/nm0.89876(14)8.9504(16)c/nm2.3030(4)2.3013(4)β/(°)95.289(2)95.170(3)Volume/nm32.2873(6)2.2699(7)Z44517291Calculateddensity/(g·cm-3)1.9441.99Absorptioncoefficient/mm-12.8253.375F(000)13281340Crystalsize/mm0.30×0.30×0.270.27×0.27×0.23θrangefordatacollection/(°)3.10to27.483.11to27.49Limitingindices-14≤h≤12,-11≤k≤11,-29≤l≤29-14≤h≤14,-11≤k≤8,-29≤l≤29Reflectionscollected2076220595Independentreflection5235(Rint=0.0357)5190(Rint=0.0289)Data/restraints/parameters5235/18/3905190/18/390Goodness-of-fitonF21.0031.002FinalRindices(I2σ(I))R1=0.0258,wR2=0.0584R1=0.0213,wR2=0.0471Rindices(alldata)R1=0.0296,wR2=0.0605R1=0.0249,wR2=0.0488Largestdifferencepeakandhole/(e·nm-3)1003and-583492and-42022.1{[Ln(Hbmdc)(bmdc)(H2O)3]·3H2O}n12，1。{[Eu(Hbmdc)(bmdc)(H2O)3]·3H2O}n(1)(1D)。H2bmdcbmdcHbmdcEu3+(Scheme1)。bmdc，212Table2Selectedbondlengths(nm)andangles(°)forcomplex1and2Complex1Eu(1)-O(10)0.2367(2)Eu(1)-O(11)0.2388(2)Eu(1)-O(7)A0.24106(19)Eu(1)-O(1)0.24341(19)Eu(1)-O(5)0.2452(2)Eu(1)-O(6)0.24818(19)Eu(1)-O(9)0.2484(2)Eu(1)-O(8)A0.24997(18)Eu(1)-O(2)0.2565(2)O(8)A-Eu(1)-O(2)111.90(6)O(7)A-Eu(1)-O(1)125.63(6)O(7)A-Eu(1)-O(5)82.91(6)O(1)-Eu(1)-O(5)81.77(7)O(11)-Eu(1)-O(8)A72.89(7)O(7)A-Eu(1)-O(8)A53.17(6)O(1)-Eu(1)-O(8)A149.49(7)O(5)-Eu(1)-O(8)A124.37(6)O(6)-Eu(1)-O(8)A138.93(6)O(6)-Eu(1)-O(2)107.83(6)O(7)A-Eu(1)-O(2)73.84(6)O(1)-Eu(1)-O(2)52.26(6)O(5)-Eu(1)-O(2)80.27(6)Complex2Dy(1)-O(10)0.23264(17)Dy(1)-O(11)0.23519(18)Dy(1)-O(7)B0.23738(16)Dy(1)-O(1)0.23933(18)Dy(1)-O(5)0.24115(17)Dy(1)-O(9)0.24474(17)Dy(1)-O(6)0.24524(17)Dy(1)-O(8)B0.24664(17)Dy(1)-O(2)0.25447(17)O(7)B-Dy(1)-O(5)82.43(6)O(1)-Dy(1)-O(5)82.60(6)O(7)B-Dy(1)-O(1)126.20(6)O(7)B-Dy(1)-O(6)133.93(6)O(1)-Dy(1)-O(6)67.90(6)O(5)-Dy(1)-O(6)54.10(5)O(8)B-Dy(1)-O(2)112.61(5)O(7)B-Dy(1)-O(8)B53.99(5)O(1)-Dy(1)-O(8)B148.93(6)O(5)-Dy(1)-O(8)B124.65(6)O(6)-Dy(1)-O(2)108.00(6)O(6)-Dy(1)-O(8)B138.19(6)O(7)B-Dy(1)-O(2)73.64(6)O(1)-Dy(1)-O(2)52.88(5)O(5)-Dy(1)-O(2)79.46(6)Symmetrytransformationsusedtogenerateequivalentatoms:1:A:-x+1,y-1/2,-z+1/2;2:B:-x+1,y-1/2,-z+1/2.Scheme1CoordinationmodesandofH2bmdcincomplex15183：髥/髥-5，6-，/；Hbmdc，1，1，。1，Eu3+63(1a)，2bmdc，1Hbmdc。Eu3+，O1、O5、O10、O9O2、O11、O7A、O8A，0.009300.01270nm，12.9°。O6。Eu-O()0.2474nm，Eu-O()0.2413nm，O-Eu-O52.26(6)°~149.68(7)°。EuO9bmdcb1D(1b)。EuEu0.6357(5)nm，Eu-Eu-Eu89.97°。，bmdc[Eu(Hbmdc)(bmdc)(H2O)3]，。。a，bmdcbmdc0.3785nm，π-π(2a)。c，(a)CoordinationenvironmentofEu髥ionatthe5%probabilitylevel;AllhydrogenatomsandfreeH2Omolecularareomittedforclarity;Symmetrycode:A:-x+1,y-1/2,-z+1/2;(b)1DchainstructureforclarityHbmdcligandsareomittedforclarity11Fig.1Viewstructureof1(a)Viewoftheleft/right-handedhelicalchainsandπ-πstackinginte