SIOC English
化学学报
高级检索

化学学报 ›› 2004, Vol. 62 ›› Issue (23): 2334-2342. 上一篇    下一篇

研究论文

[Co(aipamp或apamp)(amp)Cl][ZnCl4]两体系中四个几何异构体的合成、结构解析以及量子化学计算

温祖标1, 郭辉瑞2, 薛赛凤1, 祝黔江1, 陶朱1, 林榕光1, 罗绪强1   

  1. 1. 贵州大学应用化学研究所, 贵阳, 550025;
    2. 南京晓庄学院, 南京, 210000
  • 投稿日期:2004-01-05 修回日期:2004-04-26 发布日期:2014-02-17
  • 通讯作者: 薛赛凤,E-mail:gzutao@263.net E-mail:gzutao@263.net

C-H…π Interactions in the [Co(aipamp or apamp)(amp)Cl]2+ Systems,Their Syntheses, 2D-NMR, X-ray Structures and Energy Minimisations

WEN Zu-Biao1, GUO Rui2, XUE Sai-Feng1, ZHU Qian-Jiang1, TAO Zhu1, LIN Rong-Guang1, LUO1   

  1. 1. Institute of Applied Chemistry, Guizhou University, Guiyang 550025;
    2. Xiaozhuang College, Nanjing 210000
  • Received:2004-01-05 Revised:2004-04-26 Published:2014-02-17

PDF

356

利用单晶X射线衍射解析了[Co(aipamp)(amp)Cl][ZnCl4] (aipamp=2-[(2-氨基异丙基)氨基甲基]呲啶,amp=2-(氨基甲基)吡啶)体系中两个异构体Ⅱ的结构和[Co(apamp)(amp)Cl][ZnCl4](apamp=2-[(2-氨基丙基)氨基甲基]呲啶)体系中一异构体Ⅲ的结构.晶体Ⅰ属单斜晶系,空间群P21/n,a=1.08028(10) nm,b=1.84843(18) nm,c=1.25582(12) nm,α=90.00°,β=97.150(2)°,γ=90.00°,V=2.4881(4) nm3,Dc=1.620 g·cm-3,Z=6,F(000)=582,R=0.0361,wR=0.0974,晶胞中含4个配合物阳离子,4个[ZnCl4]2-阴离子;晶体Ⅱ 属三斜晶系,空间群 P1,a=0.9957(2) nm,b=1.0207(3) nm,c=1.1478(3) nm,α= 102.584(5)°,β=91.559(5)°,γ=98.462(5)°,V=1.1240(5) nm3,Dc=1.699 g·cm-3,Z=2,F(000)=580.00,R=0.0449,wR=0.0984,晶胞中含2个配合物阳离子,2个[ZnCl4]2-阴离子.晶体Ⅲ属三斜晶系,空间群P1,a=0.82423(7) nm,b=1.7199(8) nm,c=1.36399(1) nm,α=86.6350(10)°,β=81.7140(10)°,γ=67.6230(10)°,V=1.10278(15) nm3,Dc=1.734 g·cm-3,Z=2,F(000)=582.00,R=0.0332,wR=0.0823,晶胞中含4个配合物阳离子,4个[ZnCl4]2-阴离子.三异构体中Co3+为六配位,且配合物阳离子中具有C-H…π 结构.用一、二维核磁共振技术解析了第四个配合物在溶液中的结构,论证了该异构体属于[Co(apamp)(amp)Cl][ZnCl4]体系.4个异构体具有共同的结构特征--分子内C-H…π结构.

关键词: Co(Ⅲ)配合物, 几何异构体, 单晶结构, 13C, 1HNMR和2DNMR, 量子化学计算, C—H…π作用

The crystal structures of two isomers I and Ⅱ in [Co(aipamp)(amp)Cl][ZnCl4] (aipamp=2-[(2-aminoisopropyl)aminomethyl]pyridine, amp=2-(aminomethyl)-pyridine) system and the crystal structure of one isomer Ⅲ in [Co(apamp)(amp)Cl][ZnCl4] (apamp=2-[(2-aminopropyl)aminomethyl]pyridine, amp=2-(aminomethyl)pyridine) system have been determined by single crystal X-ray diffraction analysis.The crystal of I belongs to monoclinic system with space group P21/n, a=1.08028(10) nm, b=1.84843(18) nm, c=1.25582(12) nm, α=90.00°, β=97.150(2)°, γ=90.00°, V=2.4881(4) nm3, Dc=1.620 g·cm-3, Z=6, F(000)=582, R=0.0361, wR=0.0974.There are four complex cations which are enantiomers with a ratio of 1:1 in a unit cell.The crystal of Ⅱ belongs to triclinic system with space group P1, a=0.9957(2) nm,b=1.0207(3) nm, c=1.1478(3) nm, α=102.584(5)°, β=91.559(5)°, γ=98.462(5)°, V=1.1240(5) nm3, Dc=1.699 g·cm-3, Z=2, F(000)=580.00, R=0.0449, wR=0.0984.There are two complex cations which are enantiomers with a ratio of 1:1 in a unit cell.The crystal of Ⅲ belongs to monoclinic system with space group P1, a=0.82423(7) nm, b=1.7199(8) nm, c=1.36399(11) nm, α=86 6350(10)°, β=81.7140(10)°, γ=67 6230(10)°, V=1.10278(15) nm3, Dc=1.734 g·cm-3, Z=2, F(000)=582.00, R=0.0332, wR=0.0823.There are four complex cations which are enantiomers with a ratio of 1:1 in a unit cell.1D and 2D NMR technique analysis reveals that the fourth isomer IV belongs to the [Co(apamp)(amp)Cl][ZnCl4] system.It is common that a C—H…π interaction exists in all four complexes.

Key words: cobalt(Ⅲ)complex, geometric isomer, crystal structure, 1D and 2D NMR techniques, computational result, C—H…πinteraction