由己二酸根桥联的新颖双U形四核铜配合物：[Cu4(phen)4(NO3)2(H2O)2(adip)4／4(Hadip)4／2](NO3)2·2H2O  

A Novel Adipato-Bridged Dual U-Shaped Tetranuclear Cu(II) Complex:[Cu_4(phen)_4(NO_3)_2(H_2O)_2(adip)_(4/4)(Hadip)_(4/2)](NO_3)_2·2H_2O

作　　者：解庆范[1] 陈延民[1] 黄妙龄[1] 林碧洲[2] 

机构地区：[1]泉州师范学院化学与生命科学学院,泉州362000 [2]华侨大学材料物理化学研究所,泉州362021

出　　处：《化学学报》2008年第19期2107-2112,共6页Acta Chimica Sinica

基　　金：福建省自然科学基金(No.Z0513017)资助项目

摘　　要：邻菲罗啉、己二酸和硝酸铜在水溶液中反应得到一种新颖的四核铜配合物[Cu4(phen)4(NO3)2(H2O)2-(adip)4/4(Hadip)4/2](NO3)2·2H2O(其中H2adip=己二酸),并经元素分析,IR,UV,TG和X射线单晶衍射分析表征.该配合物晶体属三斜晶系,P1空间群,a=1.0146(2)nm,b=1.0261(2)nm,c=1.8285(4)nm,α=91.66(3)°,β=92.19(3)°,γ=112.76(3)°,V=1.7520(6)nm3,Z=1,Dc=1.639g/cm3,C66H66Cu4N12O28,Mr=1729.47,F(000)=886,μ=1.294mm-1,R1和wR2分别为0.0447和0.1141.己二酸根通过4个羧基O将两个U形双核亚单元联接成具有一个对称中心的双U形四核结构,其中每个U型亚单元包含晶体学上不对称的2个Cu(Ⅱ)原子.每个Cu(Ⅱ)离子均处于畸变的四方锥配位环境,除与己二酸氢根(Hadip)、己二酸根(adip)和邻菲罗啉(Phen)的N,O配位形成锥底平面外,其中的1个Cu(Ⅱ)与水配位,而另一个Cu(Ⅱ)则与硝酸根配位.配合物晶体结构中存在着广泛的氢键和π…π作用.A novel tetranuclear copper（Ⅱ） complex [Cu4（phen）4（NO3）2（H2O）2（adip）4/4（Hadip）4/2]（NO3）2·2H2O （H2adip=adipic acid） was isolated from the reaction of 1,10-phenanthroline （phen）, adipic acid and Cu（NO3）6H2O in water solution, and characterized by elemental analysis, IR, UV, TG and single-crystal X-ray diffraction analysis. The complex crystallizes in the triclinic system, space group P1 with a=1.0146（2）nm,b=1.0261（2）nm,c=1.8285（4）nm,α=91.66（3）°,α=92.19（3）°,γ=112.76（3）°,V=1.7520（6）nm3,Z=1,Dc=1.639g/cm3,C66H66Cu4N12O28,Mr=1729.47,F（000）=886,μ=1.294mm^-1,The final R1 and wR2 are 0.0447 and 0.1141 for 5672 observed reflections with I〉2σ（I）, respectively. It was revealed that the adipic acid groups adopt two types （syn-syn） of binding modes, an adipate bridge and two coordinated protonated adipate （Hadip）. The adipate bridge provides its four carboxylate O atoms to link two U-shaped subunits into a centrosymmetric dual U-shaped tetranuclear Cu（Ⅱ） structure. Each U-shaped frame consists of two crystallographically distinct Cu（Ⅱ） sites, in which each Cu（Ⅱ） exhibits a distorted square pyramidal geometry with the basal plane completed by two N atoms from one phen, one O atom from the adi- pate bridge and the other from the Hadip ligand. While the apical O atom in one Cu（Ⅱ） coordination sphere is from a coordinated water, that in the other Cu（Ⅱ） sphere is from a nitrate anion. There are extensive hy-drogen bonds and π…πinteractions in the crystal structure.

关 键 词：四核配合物 铜配合物 晶体结构 己二酸 柔性配体 

分 类 号：O641.4[理学—物理化学]