一个基于1,10-邻菲咯啉端基配体的己二酸桥联双核铜配合物的合成与晶体结构

通过Cu(ClO4)2与己二酸(adipate)和邻菲咯啉(phen)在甲醇-水溶剂中反应得到了一个双核配合物Cu2(phen)4(adipate)](ClO4)2.(H2O)1.33,并用元素分析、红外及X-单晶衍射技术进行了结构表征.标题化合物属于单斜晶系,C2/c空间群,晶胞参数为a=3.431 6(3)nm,b=1.380 05(12)nm,c=3.241 4(3)nm,β=94.679 0(10)o,V=15.299(2)nm3,Z=8.晶格中存在1.5个结晶学独立但结构参数非常类似的双核单元.每个中心Cu(Ⅱ)离子均处于五配位扭曲四方锥构型,配位原子分别来自于两个螯合的邻菲咯啉配体和一个己二酸根上的羧基氧原子.为了减小空间位阻效应,与中心Cu(Ⅱ)离子螯合配位的两个邻菲咯啉配体之间近似呈垂直排列.两个相邻Cu(Ⅱ)离子通过己二酸根离子连接形成双核结构,且相邻的双核单元之间存在较强的芳环堆积相互作用.

Synthesis and Crystal Structure of an Adipate-bridged Dinuclear Copper(Ⅱ) Complex with 1,10-Phenanthroline (phen) Terminal Ligands

The reaction of Cu(ClO4)2 with adipate and 1,10-phenanthroline (phen) in methanol/water solution afforded a new dinuclear coordination complex with the chemical formula of Cu2(phen)4(adipate)](ClO4)2·(H2O)1.33, which was structurally characterized by elemental analyses, IR spectrum and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system, space group C2/c with a=3.431 6(3) nm, b=1.380 05(12) nm, c=3.241 4(3) nm, β= 94.679 0(10)o, V=15.299(2) nm3, Z=8. There are one and a half crystallographically independent dinuclear cations in the lattice, however, with quite similar structural parameters. Each Cu(Ⅱ) center is penta-coordinated (CuN4O) to two chelating phen ligands and a carboxylate oxygen from adipate, displaying a slightly distorted square-pyramid geometry. The two phen ligands chelating to each Cu(Ⅱ) center arrange in almost perpendicular orientation to avoid the severe steric hindrance. The adjacent Cu(Ⅱ) ions are bridged by an adipate dianion to form a binuclear structure, and as expected, significant π-π stacking interactions between the phen ligands are observed between the dimeric units.