单羟基桥连的双铜(Ⅱ)大环穴醚配合物[Cu_2(OH)(ClO_4)(C_(16)H_(38)N_6)](ClO_4)_2·CHCl_3的合成和结构  

SYNTHESIS AND CRYSTAL STRUCTURE OF THE BINUCLEATING MACROCYCLIC MONOHYDROXO-BRIDGED DICOPPER( Ⅱ) COMPLEX [Cu_2(OH)(C10_4)(C_(16)H_(38)N_6)](C10_4)_2·CHC1_3

作　　者：金祥林[1] 童友之 刘延秋 徐筱杰[1] 唐有祺[1] 

机构地区：[1]北京大学物理化学研究所,北京100871

出　　处：《无机化学学报》1991年第1期69-75,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助的课题

摘　　要：本文合成了单羟基桥连的双铜(Ⅱ)大环穴醚配合物[Cu_2(OH)(ClO_4)(C_(16)H_(38)N_6)](ClO_4)_2 ·CHCl_3,并测定与讨论了它的晶体结构.晶体属于正交晶系,空间群为D_2~4 -P2_12_12_1,晶胞参数:a=12.749(4)(?),b=14.361(3)(?),c=18.064(3)(?),V=3307.3(13)(?)~3,Z=4。分子结构中单羟基桥连两个二价铜离子,Cu-O平均键长为1.935(6)(?),Cu-OH-Cu键角为135.2(2)°;铜原子的几何构型为畸变四方锥,配体的底面为穴醚的二乙三胺亚基的三个氮原子和一个羟基桥氧原子;顶点位置为高氯酸根的氧原子,因为该原子同时配位于另一个铜原子,所以分子的双铜中心存在第二个氧桥,即较弱的高氯酸根桥;Cu-O(ClO_3)距离分别为3.005(9)(?)和2.806(8)(?).This article reports the synthesis and structure of the binucleating macrocyclic monohydroxo-bridgcd dicopper(Ⅱ) complex [Cu2(OH)(ClO4)[A](ClO4)2 ·CHC13 (A= 1,4,7,12,15,18-hexaazacyclodocosane). The structure of complex was revealed by X-ray analysis of single crystal, orthohombic system, space group D24-212121, with a= 12.749(4)A, b=14.36'l(3)A, c=18.064(3)A, V= 3307.3(13) A3, and Z = 4. The (μ-hydroxo)dicopper(Ⅱ ) unit is characterized by short Cu-O bond lengths of 1.919 (6) and 1.951 (7)A and a Cu-OH-Cu angle of 135.2(2)° . The geometry around the copper atoms is distorted square pyramidal with the basal plane positions occupied by three ring nitrogen atoms and one hydroxide oxygen atom, and the two copper cations weakly bond the same oxygen atom of the bridging perchlorate group (Cu(l)-O(31) = 3.005(9)A, Cu(2)-O(31) = 2.806 (9) A).

关 键 词：铜 配合物 穴醚 合成 晶体结构 

分 类 号：O614.121[理学—无机化学]