新型二维异核配位聚合物{[NdBi(cydta)(NO3)2(H2O)4]·2．5H2O}n的晶体结构与热分解  

Crystal Structure and Thermal Decomposition of a 2D Heterometallic Coordination Polymer {[NdBi(cydta)(NO_3)_2(H_2O)_4].2.5H_2O}_n

作　　者：蒋琪英[1] 邓洪权[1] 胡亚敏[1] 沈娟[1] 钟国清[1] 胡宁海[2] 

机构地区：[1]西南科技大学化学系,绵阳621010 [2]中国科学院长春应用化学研究所,长春130022

出　　处：《化学学报》2008年第12期1429-1434,共6页Acta Chimica Sinica

基　　金：四川省科技厅应用基础研究基金(No.05JY029-113);西南科技大学人才引进基金;青年基金(Nos.ZK043129,ZK053012)资助项目

摘　　要：由Bi(Hcydta).5H2O和Nd(NO3).6H2O按1︰1的物质的量比,在水溶液中合成了含Bi(III)-Nd(III)的异核配位聚合物{[(NO3)Nd(H2O)4(μ3-cydta)Bi(μ-ONO2)].2.5H2O}n.用元素分析、红外光谱、热重-差热和X射线单晶衍射等手段对标题配合物的组成和结构进行了表征.该配合物属三斜晶系,空间群P1,晶胞参数:a=0.9235(3)nm,b=1.0902(4)nm,c=1.4253(5)nm,α=71.840(4)°,β=86.877(4)°,γ=76.991(4)°,Z=2,Mr=936.65,V=1.3284(8)nm3,Dc=2.342g.cm-3,μ=8.646mm-1,F(000)=900,最终偏离因子R1=0.0406,wR2=0.1124.在该配合物中,铋(III)与配体cydta4-的4O2N和1个硝酸根中1个O原子以及邻位分子的硝酸根形成8配位的畸变双帽三棱柱.钕(III)与4个水分子的O,1个硝酸根中2个O以及来自3个不同配体cydta4-的桥联羧基O结合,形成9配位的三帽三棱柱构型.羧酸根在Bi—Nd和硝酸根在Bi—Bi间的桥联作用,使得整个配合物分子连接成无限二维框架结构.热分析以及分解产物的红外光谱表明配合物热分解经历脱水、配体热分解、硝酸盐转变成氧化物等多步连续分解过程,最后在625℃失重恒定.A Bi（Ⅲ）-Nd（Ⅲ） heterometallic c-loordination polymer, {[（NO3）Nd（H2O）4（μ3-cydta）Bi- （μ-ONO2）]·2.5H2O}n, was synthesized by Bi（Hcydta）·5H2O and Nd（NO3）·6H2O at a molar ratio of 1 ： 1 in distilled water （cydta=trans-cyclohexylene-1,2-diaminetetraacetate）. The compound was characterized by elemental analysis, FT-IR, TG-DSC and X-ray single crystal diffraction. It crystallizes in the triclinic system, space group PT with a=0.9235（3） nm, b=1.0902（4） nm, c=1.4253（5） nm, α=71.840（4）°, β= 86.877（4）°, 7=76.991（4）°, Z=2, Mr=936.65, V=1.3284（8） nm3, Dc=2.342 g·cm^-3, μ=8.646 mm^-1, F（000）=900, R1 =0.0406, and wR2=0.1124. In this complex, Bi atom is octahedrally coordinated by four carboxyl O atoms and two amido N atoms from a single cydta^4- anion, and two O atoms from different two NO3^- anions, forming a distorted bicapped trigonal prism geometry. Nd atom is bonded to four O atoms from four H2O molecules, two O atoms from one NO3^- anion, and three O atoms from three bridging carboxylate groups belonging to different cydta^4- anions, resulting in nine coordination number with a tricapped trigonal prism geometry. The bridging cydta^4- between Bi-Nd atoms and NO3 between Bi-Bi atoms result in a novel infinite 2D network structure. FT-IR spectrum and DSC indicate that thermal decomposition proceeded in several stages： dehydration, pyrolysis of ligand, and final decomposition of salt, and the residue is oxide in the formula BiNdO3 at the temperature of 625℃.

关 键 词：杂核配合物 铋(Ⅲ) 钕(Ⅲ) 氨基多羧酸 晶体结构 

分 类 号：O641.4[理学—物理化学]