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机构地区:[1]淮北煤炭师范学院化学与材料科学学院,安徽淮北235000 [2]安徽大学化学化工学院,安徽合肥230039
出 处:《合成化学》2010年第1期40-43,73,共5页Chinese Journal of Synthetic Chemistry
基 金:安徽省高校自然科学基金资助项目(KJ2008B65ZC);"含能材料"安徽省重点实验室科研开放基金资助项目(KLEM2009004)
摘 要:亚甲基丁二酸、邻菲啰啉(phen)和硝酸铜在甲醇-水中反应合成了一种由亚甲基丁二酸根(IA)桥联的新颖双U形四核铜配合物[Cu4(IA)2(phen)4(H2O)4](NO3)4(H2O)6(1),其结构经UV,IR,元素分析和单晶X-射线衍射分析表征。1属三斜晶系,Pī空间群,晶胞参数a=1.2262(3)nm,b=1.282 4(3)nm,c=1.3551(3)nm,α=63.236(2)°,β=75.555(2),°γ=73.126(2)°,Z=2,F(000)=844,R=0.059 6,wR=0.166 2。IA通过8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两个Cu(Ⅱ)离子。每个Cu(Ⅱ)离子均处于畸变的四方锥配位环境,除与IA和phen的O,N配位形成锥底平面外,Cu(Ⅱ)还与水配位。A novel methylene-succinate bridged dual U-shaped tetranuclear Cu ( II ) complex [ Cu4 (IA) 2 ( phen), ( H2 O) 4 ] ( NO3 ), ( H2 O) 6 ( 1 ) was synthesized by the reaction of 1,10 -phenanthroline (phen), methylene-suceinie acid ( H2IA) and Cu (NO3 )2 · 3H2O in methanol-water solution. The structure was characterized by UV, IR, elemental analysis and single-crystal X-ray diffraction analysis. 1 belongs to triclinie system, space group PI with a = 1. 226 2 (3) nm, b = 1. 282 4 (3) nm, c = 1.355 1(3) nm, α=63.236(2)°, β =75.555(2)°, γ=73. 126(2)°, Z=2, F(000) = 844, R =0.059 6 and wR =0. 166 2. The methylene-suceinate bridge provides its eight carboxylate O atoms to link two U-shaped subunits into a centrosymmetric dual U-shaped tetranuclear Cu( II ) strueture. Each U-shaped frame consists of two distinct Cu ( II ) sites, in which each Cu ( II ) exhibits a distorted square pyramidal geometry with the basal plane formed by two N atoms from one phen and atoms from the methylene-succinate bridge. While the apical O atom in each Cu ( II ) coordination sphere is from a coordinated water.
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