化学学报 ›› 2001, Vol. 59 ›› Issue (12): 2162-2169. 上一篇    下一篇

研究论文

18-冠-6与Na2[M(mnt)2](M=Cu, Ni)配合物的合成与结构

窦建民;李大成;于清江;刘颖;徐立强;毕文华;雍伟;郑培菊   

  1. 山东省聊城师范学院化学系.;复旦大学分析测试中心.上海(200433)
  • 发布日期:2001-12-15

Synthesis nad crystal structure of 18-crown-6 complexes with Na2[M (mnt)2](M=Cu, Ni)

Dou Jianmin;Li Dacheng;Yu Qingjiang;Liu Ying;Xu Liqiang;Bi Wenhua;Yong Wei;Zheng Peiju   

  1. Shandong.;Fudan Univ, Ctr Anal & Measurement.Shanghai(200433)
  • Published:2001-12-15

研究了18-冠-6分别与Na2[M(mnt)2][M=Cu,Ni;mnt=丁二腈烯二硫醇阴离子,C2S2(CN)^2^-~2]的反应,得到的配合物{[Na(18-C-6)][Na(18-C-6)(H2O)]}[Cu(mnt)2](1),[Na(18-C-6)(H2O)]2[Ni(mnt)2].(18-C-6)(2)通过元素分析、红外光谱、X射线单晶衍射进行了表征。两个配合物均为三斜晶系,空间群P1。1的晶体学结构数据:a=1.22697(19)nm,b=1.22780(19)nm,c=1.5665(3)nm,α=95.083(3)°,β=101.534(3)°,Υ=91.007(3)°,V=2.3016(6)nm^3,Z=2,Dcalcd=1.350g/cm^3,F(000)=976,R1=0.0726,wR2=0.1843.2的晶体学结构数据:a=1.11620(17)nm,b=1.22054(18)nm,c=1.27939(18)nm,α=111.647(2)°,β=29.792(3)°,Υ=103.201(2)°,V=2.5461(4)nm^3,Z=1,Dcalcd=1.304g/cm^3,F(000)=642,R1=0.0459,wR2=0.1003.1中的[Cu(mnt)2]^2^-通过mnt的氮原子与[Na(18-C-6)]^+中的钠原子成键,形成了一维链状结构;[Na(18-C-6)(H2O)]^+只起平衡电荷的作用。2中的[Ni(mnt)2]^2^-也通过配体的mnt氮原子与两个[Na(18-C-6)(H2O)]^+中的钠原子成键,形成稳定的中性配合物。

关键词: 冠醚, 晶体结构, 铜络合物, 镍络合物, 丁二腈P, 硫醇P

Reactions of 18-crown-6(18-C-6) with Na2[M(mnt)2][M=Cu, Ni; mnt=1, 2- dicanoethene-1, 2-dithiolate, C2S2(CN)^2^-~2] were studied and the novel complexes {[Na(18-C-6)][Na(18-C-6)(H2O)]}[Cu(mnt)2](1) and [Na (18-C-6)(H2O)]2[Ni(mnt)2].(18-C-6)(2) were characterized by elemental analysis, IR and X-ray diffraction analysis. 1 and 2 belong to triclinic, space group P1 with cell dimensions: 1, a=1.22697(19) nm, b=1.22780(19) nm, c=1.5665(3) nm, α=95.083(3)°, β=101.534(3)°, Υ =91.007(3)°, V=2.3016(6) nm^3, Z=2, Dcalcd=1.350 g/cm^3, F(000)=976, R1=0.0726, wR2=0.1843 and 2, a=1.11620(17) nm, b=1.22054(18) nm, c=1. 27939(18) nm, α=111.647(2)°, β=29.792(3)°, Υ=103.201(2)°, V=2. 5461(4) nm^3, Z=1, Dcalcd=1.304 g/cm^3, F(000)=642, R1=0.0459, wR2=0. 1003. 1 Displays a one-dimensional chain of [Na(18-C-6)]^+ complex cations and [Cu(mnt)2]^2^- complex anion bridged by Na-N interactions. The complex cation [Na-(18-C-6)(H2O)]^+ serves as a balancing charge in crystal. In 2. two [Na(18-C-6)(H2O)]^+ complex cations and a [Ni (mnt)2]^2^- complex anion form a stable neutral complex through Na-N binding.

Key words: CROWN ETHER, CRYSTAL STRUCTURE, COPPER COMPLEX, NICKEL COMPLEX, BUTANENITRILE P

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