新型Cu(II)-邻菲咯啉-丁二酸三元配合物:[Cu(phen)_2L](H_2L)·5H_2O(1)和[(phen)_2CuLCu(phen)_2]L·10H_2O(2)的合成及晶体结构(H_2L=丁二酸(C_4H_6O_4))  

Syntheses and Crystal Structures of Novel Cu(II)- Phenanthroline-Succinic Acid Complexes: (H_2L)·5H_2O(1)and L·10H_2O(2) (H_2L=succinic acid, (C_4H_6O_4))

作　　者：孔祖萍[1] 郑岳青[1] 张飚[2] 金松林[2] 岳斌[2] 

机构地区：[1]宁波大学固体材料化学研究所,宁波315211 [2]复旦大学化学系,上海200433

出　　处：《复旦学报（自然科学版）》2003年第6期917-924,共8页Journal of Fudan University：Natural Science

基　　金：国家自然科学基金资助项目(20171013);浙江省自然科学基金资助项目(RC99034)

摘　　要：合成了两种新型Cu(II) 邻菲咯啉 丁二酸三元配合物,即[Cu(phen)2L](H2L)·5H2O(1)和[(phen)2CuLCu(phen)2]L·10H2O(2),它们均属三斜晶系,空间群为P1(no.2),晶胞参数分别为:(1)a=10.282(3),b=12.141(3),c=14.233(4) ,α=78.55(2)°,β=76.50(2)°,γ=84.29(2)°,V=1690.7(9) 3,Z=2,R=0.1021,wR2=0.1387;(2)a=12.943(2),b=14.436(2),c=17.974(3) ,α=75.128(9)°,β=69.030(9)°,γ=69.02(1)°,V=2896.2(9) 3,Z=2,R=0.0976,wR2=0.2240.结构分析表明,每个Cu原子与分属于2个邻菲咯啉配体的4个N原子和来自丁二酸根的2个O原子形成配位数为6的畸变八面体CuN4O2.配合物(1)中配位分子间通过芳环堆积作用形成平行[011]方向的一维超分子链,超分子链之间通过结晶水分子的氢键作用形成二维层,并进而堆积形成一维隧道和三维骨架,丁二酸分子和其余结晶水分子位于隧道内.配合物(2)中丁二酸根桥联的双核配阳离子借助芳环堆积作用形成平行于(010)面的正电性二维层,C4H4O42-离子和结晶水分子位于正电层之间并形成负电性二维网络层.Two new Cu(II)-phenanthroline-succinic acid complexes:(H_2L)·5H_2O(1)and L·10H_2O(2)(H_2L=succinic acid, (C_4H_6O_4)) have been synthesized. They belong to triclinic, space group P1(no.2), the cell parameters are: (1)a=10.282(3), b=12.141(3), c=14.233(4) ?, α=(78.55(2)°,) β=76.50(2)°, γ=84.29(2)°, V=1 690.7(9) ?~3, Z=2,R=0.102 1, wR^2=0.138 7 and (2) a=(12.943(2),) b=14.436(2), c=17.974(3) ?, α=75.128(9)°, β=69.030(9)°, γ=69.02(1)°, V=2 896.2(9) ?~3, Z=2, R=0.097 6, wR_2=0.224 0, respectively. The X-ray single crystal diffraction shows that each copper atom is coordinated with two oxygen atoms of succinato and four nitrogen atoms of two phenanthroline ligands, which forming distorted octahedron. In Complex (1), one-dimension super molecular chain is constructed by aryl π-π stacking interaction between coordinated molecules and two-dimension layer is assembled by hydrogen bonds between the chains through crystal water molecules, which further give out one-dimension tunnel and three-dimension framework. In complex (2), electropositive two-dimension layer along (010) direction is formed by aryl π-π stacking interaction between dinuclear cations bridged by succinate, conversly, electronegative two-dimension layer of succinate anions and water molecules is sandwiched between the electropositive layers.

关 键 词：铜配位物 超分子组装 合成 晶体结构 芳环堆积 

分 类 号：O614.121[理学—无机化学]