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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (6): 550-554. 上一篇    下一篇

研究简报

新型一维梯状双链配位聚合物{[Cu(malate)(2,2'-bipy)]•3H2O}∞的合成、晶体结构与表征

李东升1,2，王尧宇*,1，刘萍1，周丽君1，秦文龙1，史启祯1   

  1. (1西北大学化学系 陕西省物理无机化学重点实验室 西安 710069)
    (2延安大学化学化工学院 陕西省化学反应工程重点实验室 延安 716000)
  • 投稿日期:2004-06-15 修回日期:2004-11-23 发布日期:2010-12-10
  • 通讯作者: 王尧宇

Syntheses, Characterization and Crystal Structure of a Novel Polymeric Complex {[Cu(malate)(2,2'-bipy)]·3H2O}∞ (malate＝malate dianion) with Ladder-Shaped Double Chains Structure

LI Dong-Sheng1,2, WANG Yao-Yu*,1, LIU Ping1, ZHOU Li-Jun1, QIN Wen-Long1, SHI Qi-Zhen1   

  1. (1 Department of Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710069)
    (2 Department of Chemistry & Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yanan University, Yanan 716000)
  • Received:2004-06-15 Revised:2004-11-23 Published:2010-12-10
  • Contact: WANG Yao-Yu

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合成了铜(II)与羟基丁二酸和2,2'-联吡啶形成的配位聚合物{[Cu(malate)(2,2'-bipy)]•3H2O}∞ (其中malate＝羟基丁二酸根, 2,2'-bipy＝2,2'-联吡啶), 通过X射线衍射测定了单晶结构, 并进行了元素分析、红外光谱、紫外光谱、热分析等研究. 配合物属单斜晶系, 空间群P2(1)/c; 晶胞参数: a＝0.70132(10) nm, b＝1.9730(3) nm, c＝1.18998(16) nm, β＝94.551(3)°; Z＝2; 最终偏离因子R＝0.0483. 配合物中每个铜(II)原子与来自2,2'-联吡啶的两个氮原子和两个羟基丁二酸根的三个氧原子配位, 形成畸变的三角双锥结构单元. 每个羟基丁二酸根以R构型方式桥联两个三角双锥结构单元, 沿a轴方向无限延伸形成一维链. 两条平行链以面对面的方式重叠, 彼此吡啶环之间存在强的(-(相互作用, 加之C吡啶环—H…O羧基弱相互作用形成新颖的梯状双链结构, 比邻的梯状双链又通过分子间O羟基-H…O羧基氢键沿a轴方向共同构筑了具有隧道的三维结构.

关键词: 羟基丁二酸铜(II), 配位聚合物, 晶体结构

Copper(II) malate polymeric complex with 2,2'-bipy, {[Cu(malate)(2,2′-bipy)]•3H2O}∞, has been synthesized and characterized by means of elemental analysis, thermal analysis, IR and UV-vis spectroscopy. The single crystal X-ray diffraction study shows that the complex is monoclinic, with space group P2(1)/c, a＝0.70132(10) nm, b＝1.9730(3) nm, c＝1.18998(16) nm, β＝94.551(3)°, Z＝2 and R＝0.0483. Each Cu(II) atom is coordinated by two nitrogen atoms from 2,2'-bipy and three oxygen atoms from two different malate dianions with a distorted trigonal bipyramidal geometry. The malate dianion adopts an R conformation bridging two copper centers, giving rise to a 1-D polymeric chain along the crystallographic axis a, and two parallel 1-D chains are constituted to form a novel ladder-shaped double chain structure through (-( interactions between the pyridine rings and Cpyridine—H…Ohydroxyl weak interactions. On the other hand, the neighboring double chains are extended into a 3-D structure with channels via intramolecular Ohydroxyl-H…Ocarboxyl hydrogen bonds in the direction of axis a.

Key words: copper(II) malate, polymeric complex, crystal structure