[Co(aipamp或apamp)(amp)Cl][ZnCl_4]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

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

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P2 1/n ,a =1 0 80 2 8( 10 )nm ,b =1 84843 ( 18)nm ,c =1 2 5 5 82 ( 12 )nm ,α=90 0 0° ,β =97 15 0 ( 2 )° ,γ =90 0 0° ,V =2 4881( 4 )nm3 ,Dc=1 62 0g·cm-3 ,Z =6,F ( 0 0 0 ) =5 82 ,R =0 0 3 61,wR =0 0 974,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P 1,a =0 995 7( 2 )nm ,b =1 0 2 0 7( 3 )nm ,c =1 14 78( 3 )nm ,α =10 2 5 84( 5 )° ,β =91 5 5 9( 5 )° ,γ =98 462 ( 5 )° ,V =1 12 40 ( 5 )nm3 ,Dc=1 699g·cm-3 ,Z =2 ,F( 0 0 0 ) =5 80 0 0 ,R =0 0 44 9,wR =0 0 984,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P 1,a =0 82 42 3 ( 7)nm ,b =1 7199( 8)nm ,c =1 3 63 99( 1)nm ,α =86 63 5 0 ( 10 )° ,β =81 714 0 ( 10 )° ,γ =67 62 3 0 ( 10 )° ,V =1 10 2 78( 15 )nm3 ,Dc=1 73 4g·cm-

The crystal structures of two isomers I and II in [Co(aipamp)(amp)Cl][ZnCl 4] (aipamp=2-[(2-aminoisopropyl)aminomethyl]pyridine, amp=2-(aminomethyl)-pyridine) system and the crystal structure of one isomer III in [Co(apamp)(amp)Cl][ZnCl 4] (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 P2 1/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) nm 3, D c=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 P 1, 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) nm 3, D c=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 P 1, 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) nm 3, D c=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][ZnCl 4] system. It is common that a C—H…π interaction exists in all four complexes.