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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (19): 2107-2112. 上一篇    下一篇

研究论文

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

解庆范a 陈延民*,a 黄妙龄a 林碧洲b

  

  1. (a泉州师范学院化学与生命科学学院 泉州 362000)
    (b华侨大学材料物理化学研究所 泉州 362021)
  • 投稿日期:2008-03-31 修回日期:2008-04-30 发布日期:2008-10-14
  • 通讯作者: 陈延民

A Novel Adipato-Bridged Dual U-Shaped Tetranuclear Cu(II) Complex: [Cu4(phen)4(NO3)2(H2O)2(adip)4/4(Hadip)4/2](NO3)2•2H2O

XIE, Qing-Fan a CHEN, Yan-Min * ,a HUANG, Miao-Ling a LIN, Bi-Zhou b   

  1. (a College of Chemistry and Life Science, Quanzhou Normal University, Quanzhou 362000)
    (b Institute of Materials Physical Chemistry, Huaqiao University, Quanzhou 362021)
  • Received:2008-03-31 Revised:2008-04-30 Published:2008-10-14
  • Contact: CHEN, Yan-Min

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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, 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＝1.639 g/cm3, C66H66Cu4N12O28, Mr＝1729.47, F(000)＝886, μ＝1.294 mm－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p×××p作用.

关键词: 四核配合物, 铜配合物, 晶体结构, 己二酸, 柔性配体

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 with 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＝1.639 g/cm3, C66H66Cu4N12O28, Mr＝1729.47, F(000)＝886 and μ＝1.294 mm－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 adipate 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 hydrogen bonds and p×××p interactions in the crystal structure.

Key words: tetranuclear complex, copper(II) complex, crystal structure, adipic acid, flexible ligand