多孔配位聚合物[Cu_(1.14)(mal)_(1.14)(4,4′-bipy)_(0.57)(H_2O)_(1.14)]_∞的合成及其晶体结构

Synthesis and Crystal Structure of Porous Coordination Polymer [Cu_(1.14)(mal)_(1.14)(4,4'-bipy)_(0.57)(H_2O)V_(1.14)]_∞

以4,4′-联吡啶(4,4′-bipy),丙二酸(H2mal)和氧化铜为原料,在DMSO-H2O中合成了多孔配位聚合物{[Cu1.14(mal)1.14(4,4′-bipy)0.57(H2O)1.14]∞,1},其结构经IR和X-射线单晶衍射表征。1属四方晶系,P421c空间群,晶胞参数为:a=16.3577(7),b=16.3577(7),c=7.5755(7),V=2027.0(2)3,Z=7,Dc=1.715g.cm-3,S=1.148,Mr=299.08,F(000)=1056,μ=2.155,△ρ=0.743e.-3～-0.155e.-3。最终偏离因子R1=0.0205,wR2=0.0574。1中每个铜(Ⅱ)原子与4,4′-bipy的一个氮原子,两个丙二酸根的3个氧原子和一个水分子的氧原子配位,形成畸变的CuNO4四方锥结构单元。CuNO4四方锥通过4,4′-bipy和丙二酸根桥联形成二维的四方网状结构,层与层之间通过分子间氢键交错平行堆积形成三维多孔配位聚合物。

Porous coordination polymer, [ Cu1.14 （real） 1.14 （4,4＇-bipy） 0.57 （ H2O）1.14] ∞ （ 1 ）, was synthesized by the reaction of 4,4＇-bipyridine （4,4＇-bipy）, malonic acid （ H2mal） and CuO in DMSO - H2O. The structure was characterized by IR and single-crystal X-ray diffraction. 1 belongs to tetragonal system, space group P42^-1c with a = 16.357 7（7）A,b =16.357 7（7） A, c =7.575 5（7）A, V=2027.0（2）A^3, Z=7, Dc=1.715 g·cm^-3, S=1.148, Mr=299.08, F（000） =1 056, μ=2.155, Δp=0.743 e·A^-3- -0.155 e·A^-3, R1=0.0205, wR2=0.0574. Each Cu（II） atom is coordinated by one nitrogen atom from 4,4＇-bipy, three oxygen atoms from two different malonate ligands and one oxygen atom from H2O with a distorted square-pyramid configuration. The resuiting CuNO4 square-pyramid is. bridged by 4,4＇-bipy and malonate ligands, forming 2D networkes. The 2D networkes are stacked parallel but in a staggered manner by intramolecular hydrogen bonds.