由间苯二甲酸和喹喔啉类配体构筑的一维隔髤的配合物的水热合成及晶体结构

由间苯二甲酸和喹喔啉类配体构筑的一维隔髤的配合物的水热合成及晶体结构 由间苯二甲酸和喹喔啉类配体构筑的一维 隔髤的配合物的水热合成及晶体结构 第27卷第10期 2011年10月 无机化学 CHINESEJ0URNAL0FIN0RGANICCHEMISTRY Vo1.27No.10 2076.2080 由间苯二甲酸和喹喔啉类配体构筑的一维隔(?) 的配合物的水热合成及晶体结构 王蕾倪良朱种黄艳菊 (江苏大学化学化工学院,镇江212003) 摘要:采用水热法合成了一种金属一有机配合物 [Cd(ipt)(Medpq)](H2ipt=isophthalicacid,Medpq=2.methyldipyrido[3,2-f:2,3'-h] quinoxaline),并对其进行了元素分析,红外光谱,紫外一可见光谱,热重表征,和X.射线单晶衍射测定.该配合物属于单斜晶系, C2lc空间群.在晶体结构中,Cd(?)原子为六配位与来自于间苯二甲酸配体上的4个羧基氧原子.及Medpq配体上的2个氮原子 配位,呈现畸变的八面体构型.整个晶体由ipt.Cd.medpq单元组成一维结构. 关键词:配位聚合物;间苯二甲酸;晶体结构;水热合成 中图分类号:0614.2442文献标识码:A文章编号:1001.4861(2011)10—2076.05 HydrothermalSynthesisandCrystalStructureofaOne-DimensionalCadmium(H) ComplexthIsophthalicAcidand2-Methyldipyrido[3,2-f:2,3'-h]quinoxalineLigands WANGLeiNILiangZHUChongHUANGYan.Ju (SchoolofChemht~andChemicalEngineering,jiangsueZhenjiang,伽M212013,China) Abstract:Ametal—organiccoordinationpolymer[Cd(ipt)(Medpq)](H2ipt=isophthalicacid,Medpq=2一 methyldi. pyrido[3,2一 f:2,3'-h]quinoxaline)hasbeenhydrothermallysynthesizedandstructurallycharacterizedb yelemental analysis,IRspectrum,UV.Visspectrum,TGandsingle.crystalX— raydiffraction.Titlecompoundcrystallizesin themonoclinicsystem,spacegroupC2/c,witha=2.0136(4)nm,b=1.6089(3)nm,c=1.6093(3)nm,fl=125.12(3)., V=4.3028(15)nm,C23H18N406Cd,M~=558.81,D=1.725g?cm,Z=8,thefinalR=0.0531andwR=O.1403.Inthe crystalstructure,thecadmiumiSsix— coordinatedwithfourcarboxylateoxygenatomsfromthreedifferent carboxylategroups,andtwonitrogenatomsfromMedpqligand,showingaslightlydistortedoctahedralgeometry. Furthermore,itexhibitsaone—dimensionalzigzagstructurewithipt— Cd.medpqasbuildingunits.CCDC:800998. Keywords:coordinationpolymer;isophthalieacid;crystalstructure;hydrothermalsynthesi s 0Introduction Therationaldesignandsynthesisofmetal—organic frameworks(MOFs)arecurrentlyofgreatinterestand importantinproducingnewfunctionalmaterials[1_8].In therecentyearssomestudieshavedealtwiththe coordinationpropertiesof1,10一phenanthroline(phen) 收稿日期:2011-03—08.收修改稿日期:2011-06.23. 江苏省研究生创新计划(N0.CXLXll一0581)~目. 通讯联系人.E-mail:niliang@ujs.edu.cn anditsderivativesintheconstructionofmetalorganic complexes.固.However,Medpq(2-methyldipyrido[3,2一f: 2,3-h]quinoxaline)asanimportantphenderivative hasbeengivenfarlessattention.Ontheotherhand, isophthalicacid(H2ipt)asarigidandversatilebridging ligandmaygeneratemulti—dimensionalstructures[9-. Inspiredbytheaboveconsiderations,weselected 第1O期王蕾等:由间苯二甲酸和喹喔啉类配体构筑的一维隔(?)的配合物的水热 合成及晶体结构2077 typicalCd(1)centerwithdistinctcoordinationprefere— ncestoassemblewithMedpqandisophthalicacid, adoptedahydrothermaltechniqueandsuccessfully synthesizedanovelcoordinationpolymers[Cd(ipt) (Medpq)]. 1Experimental 1.1Materials TheMedpqligandwassynthesizedaccordingto theiteraturemethod~71.Cd(CH3COO)2?2H2Oand isophthalicacidwerepurchasedcommerciallyandused withoutfurtherpurification. 1.2Instrumentandmeasurements TransmissionmodeFTIRspectrumwasobtained between4000and400cm一usingaNicoletNexus470 infraredspectrometer.Elementalanalysiswasca~ied outwithaPerkin—Elmer240Canalyzer.Thermogravi— metricanalysis(TG)anddifferentialscanningcalori— metric(DSC)analysisoftheprecursorpowderswas performedonaGermanyNetzschSTA449Cwith heatingrateof10oC?min,underflowingnitrogen.UV— VisabsorptionspectrumwasrecordedonaHitachiUV一 2450spectrophotometeratroomtemperature. 1.3Synthesisofthetitlecomplex Thecompound[Cd(ipt)(Medpq)]wasprepared fromamixtureofCd(CH3C00)2?2H20(0.267g,1 mmo1),H2ipt(0.166g,1mmo1),Medpq(O.248g,1mmo1) andH20f8mE)inan18mLTenon—linedautoclave underautogenouspressureat165?forfivedays.After coolingtoroomtemperature,Yellowblockcrystalsof [Cd(ipt)(Medpq)lwerecollectedbyfiltrationand washedwithdistilledwaterin60%yieldfbasedonCd). Ana1.Calcd.forC23H18N4O6Cd(%):Cd,20.11;C,49.42; H,3.26;N,10.04;O,17.17.Found(%):Cd,20.12;C, 49.43;H,3.25;N,10.03;0,17.18.IR(KBr,cm):3370 HIfrespectivelyascribedtothestretchingvibrationsof H20.whichindicatestheexistenceofwatermolecules). 1600s.l550s,1440s.1370sl080s.823s.729s. 1.4Structuredetermination Asinglecrystalwithdimensionsof0.2mmx0.2 minx0.2mmwasmountedonaBrukerSmartApexI1 CCDdiffractmeterequippedwithagrahite??monochro-- maticMoKaradiation=0.071073nm)byusingan 一 scanmode(5.94.<20<50.7.)at293(2)K.The structurewassolvedbydirectmethodswithSHELXS一 97program[羽andrefinedbySHELXL一97【9】usingfull— matrixleast-squarestechniquesonF.Allnon-hydrogen atomswererefinedanisotropicallyandhydrogenatoms isotropically.AllHatomswerepositionedgeometrically (C-H0.093nmforCHor0.096nmforCH3)andrefined asridingmode,with(H)ValUeSof1.2(c).The detailedcrystallographicdataandstructurerefinement parametersforthetitlecomplexaresummarizedin Table1. CCDC:800998 Table1Crystallographicdataforthetitlecomplex EmpiricalformulaC?H1sN406Cdc/nm1.6093(3) Formulaweight558.81卢/(.)125.12(3) D/(g-cm-3)1.725V/nm4.3028(151 /.t(MoK0./BIT[1.065Z8 CrystalsystemMonoclinicR1,wR2(1>2o-(/))0.0531,0.1403 SpacegroupC2/c00o12240 Crystalsize/mmO.20x0.20x0.20Collectedreflections9939 a/nm2.0316(4,Goodness—of-fit(GOF)onF1.052 b/nm1.6089(3) 2Resultanddiscussion 2.1Descriptionofcrystalstructure Single?-crystalX-?raydiffractionanalysisreveals thatcompound[Cd(ipt)(Medpq)]crystallizesinC2/c spacegroupandconsistsofaone—dimensionalzigzag chainstructure.Theminimumasymmetricunitofthe compound[Cd(ipt)(Medpq)]isshowninFig.1.There areoneCd(?)ion,oneiptligand,oneMedpqligand andtwodissociatingwatermoleculesintheasymmetric 2078无机化学第27卷 unit.TheCd(11)ionissix—coordinatedwithsixatoms (N(1),N(2),O(1),O(2),O(3),O(4))fromMedpqligand andiptligand,showingaslightlydistortedoctahedral geometry.Theselectedimportantbondparametersare giveninTable2.Inthecompound[Cd(ipt)(Medpq)] eachipt一ligandlinksthreeCd(1I)ionsbymeansof bridgingandchelatingcoordinationmode,andthe adjacentCdatomsarebridgedthroughipt一ligandsto obtainaonedimensionalzigzagchainalongtheaaxis, asshowinFig.2. c17c18 4C19 C22.C o 9 — N4C15 Cl3 C14 Fig.1ORTEPdrawingof【Cd(ipt)(Medpq)]showingthe localcoordinationenvironmentofCd(Dwith thermalellipsoidsat30%probability Intheone—dimensionalinfinitechains, intermoleeular7r-7rstackinginteractionsarefound betweenthearomaticringofMedpqanditsequivalent Fig.2One—dimensionalzigzagchainstructureof [Cd(ipt)(Medpq)lshowing7r一7rstacking interactions symmetryat(1一,Y,1/2-z)inanoffsetfashion.The distancesforface..tofaceandcentroid..tocentroid are0.3616and0.3672nm.respectively.Therelative dihedralanglesrangefrom0.to2.30..allofwhichfall inthereportednormalrange[~2".The7r一7rstacking interactionsextendalongtheaaxis,thusformingthe titlecompoundwitha2Dlayerstructure.Incompound [Cd(ipt)(Medpq)]hydrogenbondsarealsoobserved betweenO(1w)andO(2W).Withthehelpofthese hydrogenbonds,the2Dlayersspreadalongtheaxes, resultinginpolymer[Cd(ipt)(Medpq)]inaninfinite3D supramolecularstructure,andthehydrogenbondsof thecompound[Cd(ipt)(Medpq)]areshowninTable3. Furthermore.the仃-7rstackinginteractionsandhydro- genbondsenhancethestabilityofthepolymert=-u1. Table2Selectedbondlengths(nm)andangles(.)fortheriflecomplex Symmetrycodes:A:x+l/2,Iy+1,2,z+l/2;B:+l/2,+1/2,-z+l;C:一1/2,+1/2,一1/2. Table3Hydrogenbondparametersfortheriflecomplex Symmetrycode:A:—,-z+l/2;B:,—y+1,一1,2. 2.2Thermalanalysis TheTGcurveof【Cd(ipt)(Medpq)]isshowninFig 3.Itshowsthatthefirstweightlossof4.5%from8O? to170?correspondstotheremovalofcoordination ? 第10期王蕾等:由间苯二甲酸和喹喔啉类配体构筑的一维隔(?)的配合物的水热 合成及晶体结构2079 watermoleculeswhichareoutoforderfcalcd.6.45%). Uponfurtherheating,anobviousweightloss(32.67%) occursinthetemperaturerangeof390-458c(=. correspondingtothereleaseoftheMedpqligand (calcd.44.38%).Obviousweightloss(22.13%)occurs inthetemperaturerangeof470~1200.corresponds tothereleaseoftheiptligand(calcd.29.37%).No weightlossisobservedafter1000cI=.indicatingthe completedecompositionof[Cd(ipt)(Medpq)].The residualweight40.7%(calcd.19.8%)correspondsto CdNandCdO. 110 1OO 80 70 50 40 200 Tf'c Fig.3TGcurv~ofthecomplex[Cd(ipt)(Medpq)] 2.3UV-Visspectrumanalysis Thecompoundof【Cd(ipt)(Medpq)]ischaracter- izedbyUV-Visspectrumatroomtemperatureinsolid state,asshowninFig.4.Theexperimentalbandsinthe 200-343nmregionresultfromligand—metalcharge transferandligand—ligandchargetransfertransitions. Theabsorptionbandat427nmisassignedtothe electronictransitionsfmetal—ligandchargetransfer)?. Theresultsindicatethegoodopticalqualityofthe compound【Cd(ipt)(Medpq)]. \ Wavelength/IMn Fig.4UV—Visspectrumofthecomplex【Cd(ipt)(Medpq)] 3Conclusions Insummary,wehavepreparedametal—organic polymersbythecombinationofisophthalicacidand2. methy1dipyrido【3,2一f:2,3'-h]quinoxalineligands,ithas beenhydrothermallysynthesizedandstructurally characterizedbyelementalanalysis,IRspectrum,UV— Visspectrum,TGandsingle—crystalX—raydiffraction. OurresearchdemonstratesthatthenewligandMedpq couldbeapotentialbuildingblocktoconstructnovel coordinationpolymerswithunusualarchitecturesand interestingphysicalproperties. [11BiradhaM,FujitaM.DaltonTram.,2000:3805—3810 [2】Kepe~CJ,RosseinskyM.Chem.Commun.,1999:375—376 【3】LIAOQiu—Xia(廖秋霞),YAOYun—Gen(~云根).Chinese Struct.Chem.(JiegouHuaxue),2006,25:465.468 【4】BattenSR,RobsonR.Angew.Chem.Int.Ed.,1998,37:1460一 】494 [5]MowtonB,ZaworotkoM. 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[201JaniakC.DaltonTram.,2000:3885—3896 [21]LIUHe(刘和),HANXiang.Yu(韩翔宇),ZHANGYan—Ping (张燕平),eta1.ChineseStruct.Chem.(JiegouHuaxue), 2006,25:547—552 【22]SUNYun(孙云),LIUXiao—Hong(~lJ晓红),ZHANGXin(~ 欣),eta1.ChineseStruct.Chem.(JiegouHuaxue),2004,23: 803—807 【23]JIANGNing—Yi(蒋宁懿),LISong—Lin(~松林).Chinese Struet.Chem.(JiegouHuaxue),2006,25:957—964 【24]JIANGNing—Yi(蒋宁懿),LISong—Lin(~松林).ChinesetJ= Struct.Chem.(JiegouHuaxue),2007,26:199—205 [25]MachuraB,KruszynskiR,JaworskaM,eta1.Polyhedron, 2006,25:25372549 欢迎订阅《无机化学》 2012年全国报刊杂志征订工作已经开始,敬请向贵单位推荐订阅2012((~机化学》 《无机化学》是由中国科协主管,中国化学会主办,南京大学化学化工学院和配位 化学 研究所承办的基础性学术期刊,面向国内外发行.设有综述,研究快报和论文等栏 目.报道无机 化学领域的基础研究和应用基础研究的创新成果,内容涉及固体无机化学,配位化 学,无机材 料化学,生物无机化学,有机金属化学,理论无机化学,超分子化学和应用无机化学,催化等着 重报道化合物的合成,结构,成键,谱学和热力学,动力学性质等 《无机化学》编辑委员会由5O位学术造诣深厚的化学家组成.其中中国科学院院士22 位.游效曾院士担任主编. 《无机化学》已被美国《科学引文索引》(SCI—E)网络版,美国《化学文摘》(CA),《中国学 术期刊文摘》(中,英文版),《中国科技论文与引文数据库(CSTPCD)},《中国科学引文数据库》, 《中文科技期刊数据库》,《中国期刊全文数据库》,《中国核心期刊(遴选)数据库》等国内外多种 着名检索刊物和文献数据库摘引和收录本刊由中国科协精品科技期刊示范项目资助出版.曾 多次荣获"百种中国杰出学术期刊"称号.是读者公认的我国重要的核心学术期刊.有极高的学 术价值和优良的编辑出版质量热忱欢迎广大作者向《无机化学》投稿 《无机化学》为月刊,大16开本,铜版纸印刷,每册200页2012年定价28.00元/册.全 年336.00元.国内邮发代号28—133,欢迎国内读者到当地邮局订阅,国外读者可通过中国国际 图贸易总公司订阅若通过邮局订阅有困难或错过订阅,请直接与编辑部联系 竭诚欢迎广大科技工作者,科研单位,高等院校,图书馆订阅 通讯地址:南京市南京大学化学楼 电话:025—83592307 网址: 邮编:210093 传真:025—83592307 E-mail:wjhx@nju.edu.an 《无机化学》编辑部