化学学报 ›› 1997, Vol. 55 ›› Issue (6): 539-544. 上一篇    下一篇

研究论文

具有两种不同配位隔室的含酚桥基'N~5O~2' Schiff碱大环铜钠 异双核配合物的 合成及结构

马长勤;张文兴;王绪宁;蒋德华   

  1. 山东大学化学学院.济南(250100)
  • 发布日期:1997-06-15

Synthesis and structure of Cu(Ⅱ) and Na(I) heterodinuclear complex of phenol-bridged 'N~5O~2' schiff base ligand with two different coordination compartments

Ma Changqin;Zhang Wenxing;Wang Xuning;Jiang Dehua   

  1. Shandong Univ., College of Chem.Jinan(250100)
  • Published:1997-06-15

以Cu^2^+和Na^+同时作为模板,用2,6-二甲酰基对甲苯酚直接与一定比例的乙二胺,二-1,2-亚乙基-三胺发生[2+2]型Schiff碱缩合,合成了含两个不同隔室Schiff碱大环配体(L^2^-)的铜钠异双核配合物[CuNaL(ClO~4)]。并对它进行了元素分析,UV-Vis,IR,^1HNMR,摩尔电导和ESR谱等项表征。ESR谱显示三个g值峰,对应的g~x,g~y,g~z值分别为1.987,2.168,2.233。单晶X射线四圆衍射分析表明,该配合物为单斜晶系,空间群P2~1/n,晶胞参数a=0.9255(3),b=1.7689(2),c=1.6055(2)nm,β=101.69(2)ⅲ,Z=4,V=2.574nm^3。Cu原子和Na原子分别位于大环配体L^2^-的'N~2O~2'四配位和'N~3O~2'五配位隔室。Cu^2^+的配位数为4,基本保持平面构型。Cu-O和Cu-N平均键长分别为0.1911,0.1926nm。Na^+除与L^2^-配位外,还与单齿高氯酸根结合,配位数为6。Na-O和Na-N的平均键长分别为0.2379,0.2468nm。Cu...Na间距离为0.3227nm。

关键词: 双核配合物, 钠, 铜, 大环, SCHIFF碱, 乙二胺, 对甲苯酚, 甲酰基, 晶胞, X射线衍射分析

The title complex [CuNaL(ClO~4)] of a Robson macrocycle with two different coordination compartments H~2L, derived from Schiff base condensation of 4-methyl-2, 6-diformylphenol and two kinds of diamine, has been synthesized in one template reaction. The complex has been characterized by UV-Vis, IR, ^1H NMR and ESR spectra. The ESR spectrum shows three peaks at g~x=1.987, g~y=2.168 and g~z=2.233, respectively. The complex crystallizes in the monoclinic crystal system, space group P2~1/n, with Z=4, a=0.9255(3), b=1.7689(2), c=1. 6055(2)nm, β=101.69(2)ⅲ, and V=2.574nm^3. The refinement converges with R=0.053 and R~w=0.065 for 2640 reflections with I≥3σ(I). The Cu(Ⅱ) and Na(I) ions reside at the 4- and 5-coordination compartments of the macrocycle, respectively. The coordination geometry around the copper atom is regarded as a planar square. But the sodium atom is also coordinated with one oxygen atom of a perchlorate anion on the axis. This geometry of six-coordinate sodium may be considered as a pentagonal pyramid. The distance between Cu and Na bridged by two phenolic oxygens is 0.3227(3)nm.

Key words: DINUCLEAR COMPLEX, SODIUM, COPPER, ETHANEDIAMINE, FORMYL, UNIT CELL, X-RAY DIFFRACTION ANALYSIS, CRYSTAL STRUCTURE

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