化学学报 ›› 2001, Vol. 59 ›› Issue (3): 405-412. 上一篇    下一篇

研究论文

过渡金属-4, 4'-联吡啶配合物的合成及其晶体结构

梁福沛;陈自卢;胡瑞祥;梁宏;郁开北;周朝晖   

  1. 广西师范大学化学系.桂林(541004);中国科学院成都分析测试中心.成都 (610041);厦门大学化学系.厦门(361005)
  • 发布日期:2001-03-15

Syntheses and crystal structures of the complexes of transition metal with 4, 4'-bipyridine

Liang Fupei;Chen Zilu;Hu Ruixiang;Liang Hong;Yu Kaibei;Zhou Chaohui   

  1. Guangxi Normal Univ, Dept Chem.Guilin(541004);Chengdu Center of Anal & Measur, CAS.Chengdu(610041);Xiamen Univ, Dept Chem.Xiamen(361005)
  • Published:2001-03-15

由过渡金属与4,4'-联吡啶反应,得到两种新型配合物[Zn(4,4'-bpy)~2(H~2O)~2](pic)~2·(4,4'-bpy)·(H~2O)(1)与[Cu(4,4'-bpy)(pic)~2](2)(4,4'bpy:4,4'-联吡啶,pic^-:苦味酸根),进行了元素分析、红外光谱、X射线衍射等表征。X射线衍射结果表明,晶体1属单斜晶系,空间群为C~c,晶胞参数为:a=2.2716(2)nm,b=1.6191(3)nm,c=1.6166(2)nm,β=131.085(7)°,V=4.481(2)nm^3,Z=4;该配合物由4,4'-联吡啶与金属配位形成多孔的二维网,二维网再由未配位的4,4'-联吡啶通过氢键作用沿a方向堆积得三维网状结构,未配位的4,4'-联吡啶、水、苦味酸根离子就被包含在这种网络之中,展示出一定的包合现象,晶体2属三斜晶系,空间群为P1,晶胞参数为:a=0.6100(2)nm,b=1.0186(3)nm,c=1.1046(2)nm,α=107.230(10)°,β=101.992(2)°,γ=97.87(7)°,V=0.6266(3)nm^3,Z=1。在该配合物中,4,4'-联吡啶分子、苦味酸根离子均与铜离子配位,形成一维链状结构。

关键词: 联吡啶, 晶体结构, 苦味酸, 锌络合物, 铜络合物, 包合物, 元素分析, X射线衍射分析

Reactions of transition metal picrates with 4, 4'-bipyridine gave two complexes [Zn(4, 4'-bpy)~2(H~2O)~2](pic)~2·(4, 4'-bpy)·(H~2O) (1) and [Cu(4, 4'-bpy) (pic)~2] (2) (4, 4'-bpy=4, 4'-bipyridine, pic^ =picric anion), which were characterized by elemental analysis, IR spectroscopy and X-ray diffraction. Complex 1 crystallizes in the monoclinic space group C~c with cell parameters a=2.2716(2) nm, b=1. 6191(3) nm, c=1.6166(2) nm, β=131.085 (7)°, V=4.481(2) nm^3, Z=4. AN infinite 2-D network structure of the complex was constructed by coordination of zinc to 4, 4'-bpy. The most interesting feature is that the 2-D network is extended into 3-D network structures by uncoordinated 4, 4'-bpy via hydrogen bonds along the a axis. All the uncoordinated 4, 4'-bpy, picric anion and water molecles are clathrated in the network, exhibiting a certain inclusion phenomenon. Complex 2 crystallizes in the triclinic space group P1 with cell parameters a=0.6100(2) nm, b=1.0186 (3) nm, c=1.1046 (2) nm, α=107. 230(10)°, β=101.992(2)°, γ=97.87(7)°, V=0.6266 (3) nm^3, Z=1. In the complex, the coordination of copper cation to 4, 4'-bipyridine and picric anion simultaneously results in the infinite one dimensional 4, 4'-bpy-bridged polymeric [Cu(4, 4'-bpy) (pic)~2] chains.

Key words: BIPYRIDINE, CRYSTAL STRUCTURE, TRINITROPHENOL P, ZINC COMPLEX, COPPER COMPLEX, CLATHRATES, ELEMENTAL ANALYSIS, X-RAY DIFFRACTION ANALYSIS

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