化学学报 ›› 2000, Vol. 58 ›› Issue (9): 1131-1135. 上一篇    下一篇

研究论文

[Cu(C~1~2H~8N~2)(H~2O)(C~4H~4O~4)]·2H~2O的合成和晶 体结构

郑岳青;孙杰;林建利   

  1. 宁波大学固体材料研究所
  • 发布日期:2000-09-15

Synthesis and crystal structure of [Cu(C~1~2H~8N~2)(H~2O)(C~4H~4O~4)] ·2H~2O

Zheng Yueqing;Sun Jie;Lin Jianli   

  • Published:2000-09-15

将适量邻菲啰啉、丁二酸和CuCl~2·2H~2o(摩尔比=1:1)溶于水和甲醇的混合溶剂[V(水):V(甲醇)=1:1]后,滴加NaOH溶液至pH=4.8。滤去沉淀物后,滤液于室温下缓慢蒸发得蓝色细长[Cu(C~1~2H~8N~2)(H~2O)(C~4H~4O~4)]·2H~2O晶体。晶体属三斜晶系,P1(No.2)空间群。晶胞参数a=0.7462(1)nm,b=(0.9959)1nm,c=1.2266(1)nm,α=75.02(1)°,β=82.38(1)°,γ=74.76(1)°,V=0.8475(2)nm^3,Z=2,D~c=1.622g·cm^3,F(000)=426.3882个独立衍射点中,2789个可观测点满足F~0^2≥2σ(F~0^2),R=0.0450,wR^2=0.0951。配合物内每个Cu与邻菲啰啉螯合配体中的2个N原子、来自不同羧酸根的2个羧基O和1个水分子O原子配位,形成扭曲的四方锥体,其中一羧基O位于锥顶[d(Cu-N)=0.2006(3),0.2032(3)nm;赤道d(Cu-O)=0.1972(2),0.1973(2)nm;轴向d(Cu-O)=0.2210(2)nm]。双齿桥联丁二酸根连接Cu原子形成平行于[100]方向的多聚超分子链^1~∞[Cu(phen)~2(H~2O)·(C~4H~4O~4)~2~/~2]~2。芳环堆积间距交替为0.366nm和0.380nm。未配位的H~2O分子位于超分子双链之间。

关键词: 铜络合物, 晶体结构, 二氮杂菲, 丁二酸, 超分子结构

blue slender crystals of [Cu(C~1~2H~8N~2)(H~2O)(C~4H~4O~4)]·2H~2O were obtained from the solution of CuCl~2, 1,10-phenanthroline, succinic acid and NaOH in CH~3OH/H~2O solution. The crystal structure was determined by single crystal X-ray diffraction. The title complex crystallized in the triclinic space group P1(No.2) with a=0.7462(1) nm, b=(0.9959)1 nm, c=1.2266(1) nm, α=75.02(1)°, β=82.38(1)°,γ =74.76(1)°, V=0.8475(2) nm^3, Z=2, D~c=1.622 g·cm^3, F(000)=426, R=0. 0450, wR^2=0.0951 for 2789 observed reflections F~0^2≥2σ(F~0^2) out of 3882 unique reflections. The crystal structure consists of supramolecular double chains ^1~∞[Cu(phen)~2(H~2O)·(C~4H~4O~4) ~2~/~2]~2 and water molecules, in which each Cu atom is square- pyramidally coordinated by two N atoms of one chelating phen ligand, two O atoms of different bidentate bridging C~4H~4O~4^2^- ligands and one O atom of water molecule with one carboxyl O atom at the apical position [d(Cu-N)=0.2006(3), 0.2032(3)nm; basal d(Cu-O)=0. 1972(2), 0.1973(2)nm; axial d(Cu-O)=0.2210(2)nm]. The twisted C~4H~4O~4^2^- ligands interlink square-pyramidally coordinated Cu atoms to form supramolecular chain ^1~∞[Cu(phen)~2(H~2O)·(C~4H~4O~4) ~2~/~2]~2 with phen ligands extended outwards on one side to form pitches.

Key words: COPPER COMPLEX, CRYSTAL STRUCTURE, PHENANTHROLINE, BUTANEDIOIC ACID, SUPERMOLECULAR STRUCTURE

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