{[(K·TPPO·DB18C6)_2(C_4H_8O_2)](HgI_3)_2}·3C_4H_8O_2单晶的合成、性质和结构表征  

Studies on Synthesis, Characterization and Structure of the Compounds { [ (K·TPPO·DB18C6)_2(C_4H_8O_2) ] (HgI_3)_2}·3C_4H_8O_2

作　　者：蒋德华[1] 刘学勇[1] 孙大岩 沈静兰[1] 

机构地区：[1]山东大学化学院,济南250100

出　　处：《化学学报》1996年第9期874-881,共8页Acta Chimica Sinica

摘　　要：用二苯并-18-冠-6(DB18C6)和三苯基氧化膦(TPPO)的三氯甲烷溶液从KI介质中萃取Hg(Ⅱ),先制得固体协萃配合物,在二氧六环(C_4H_8O_2)中重结晶得标题物单晶,对单晶进行了熔点测定、热重和红外光谱分析,测定了结构.晶体属P(?)空间群,晶胞参数a=1.4211(2),b=1.4488(4),c=1.4934(4)nm;α=113.61(2),β=110.78(1),γ=87.29(2)°.晶体中每个K与一个DB18C_6上的六个O和一个TPPO上的一个O配位的同时,每两个K还与一个C_4H_8O_2上的两个O配位,桥连成中心对称的二聚[(K·TPPO·DB18C_6)_2(C_4H_8O_2)]^(2+)配阳离子;每两个Hg通过两个Ⅰ桥连成二聚[HgI_3]_2^(2-)配阴离子;阴阳离子相间排列.另外三个C_4H_8O_2分子填充于晶格间隙中.The crystals of the title compounds were synthesized by solvent extraction of Hg(II) with DB18C6 and TPPO in CHCl3 solution from KI media,and recrystallization in C4H8O2. They have been studied by melting point determination and TG, IR analysis,and have been structurally characterized by singlecrystal X - ray diffraction techniques. Crystals of the complexes are triclinic,space group P 1 with a = 1.4211 (2), b = 1. 4488(4), c = 1. 4934(4)nm; α = 113. 61(2),β= 110. 78(1), γ = 87. 29(2)°. In the crystals,every K is coordinated by the six oxygen atoms of the DB18C6,one oxygen atom of the TPPO, and every two K are coordinated by twooxygen atoms of the C4H8O2. Dipolymer [ (K·TPPO·DB18C6)2 (C4H8O2) ]2+ cations can beconsidered to be based on a centrosymmetric bridged dimetric arrangement. Every two Hg were halogen - bridged by two I to be a dipolymer (HgI3)22- anions. The anions and the cations arrange in order every other. The other three C4H8O2 fill in the gap of the lattices.

关 键 词：萃取 三苯基氧化膦 单晶 DB18C6 TPPO 晶体结构 

分 类 号：O614.243[理学—无机化学]