过渡金属-4, 4'-联吡啶配合物的合成及其晶体结构

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。

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

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.