四核银簇合物Ag_4(o-CH_3C_6H_4CS_2)_4(Py)_4与二核铜化合物Cu_2(o-CH_3C_6H_4CSS_2)_2(Py)_2的合成和晶体结构

邻甲基苯荒酸四乙基铵盐分别与硝酸银和氯化铜反应,经毗啶重结晶,得到四核银簇合物Ag_4(o-CH_3C_6H_4CS_2)_4(Py)_4(晶体Ⅰ)和二核铜化合物Cu_2(o-CH_3-C_6H_4CSS_2)_2(Py)_(晶体Ⅱ)。用X射线单晶衍射法测定了它们的晶体结构。晶体Ⅰ的空间群为P2/n。晶胞参数:a=14.757(4),b=12.231(3),c=15.183(4)A,β=91.14(2)°,V=2739.95A~3,Z=2。2590个衍射点参与修正,最终偏差因子R=0.087。晶体Ⅱ的空间群为C_1~1-P1。晶胞参数:a=9.307(7),b=9.546(7),c=10.119(8)A,α=95.06(9),β=109.74(10),γ=118.86(10)°,V=705.94A~3,Z=1。1198个衍射点参与修正,最终偏差因子R=0.086。 Ag_4(o-CH_3C_6H_4CS_2)_4(Py)_4分子中Ag_4呈蝴蝶状构型,其配位情况与四核银簇合物Ag_4(a-C_(10)H_7CS_2)_4(Py)_4相似。Cu_2(o-CH_3C_6H_4CSS_2)_2(Py)_2分子构型与Cu_2(a-C_(10)H_7CSS_2)_2(Py)_2十分相似。Cu—Cu键长为2.608A。而且邻甲基苯荒酸与Cu~(2+)反应包括一个氧化还原反应,也与a-萘荒酸与Cu~(2+)反应相似。可以认为邻甲基苯荒酸与a-萘荒酸有相似的空间效应和电子效应。

The Syntheses and Crystal Structures of Tetranuclear Silver Cluster Complex Ag_4(o-CH_3C_6H4_CS_2)_4(Py)_4and Dinuclear Copper Complex Cu_2(o-CH_3C_6H_4CSS_2)_2(Py)_2

The products of reactions between tetraethylammonium o-methyl-dithioben-zoate and AgNO3 or CuCl2 were recrystallized from pyridine to give Ag4 (o-CH3C6H4CS2)4(Py)4(Crystal I) and Cu2(o-CH3C6H4CSS2)2(Py)2(Crystal Ⅱ)respectively. Their crystal structures were determined by a singlecrystal X-ray diffraction analysis. The crystal I belongs to space group P2/n with unit cell parameters: a=14.757(7),b = 12.231(3), c=15.183(4)A,β=91.14(2)°,V=2729.95A3, Z = 2, R= 0.087 for 2590 reflections. The crystal II belongs to space group C11-P1, with unit cell parameters, a=9.307(7)A, b=9.546(7)A,c = 10.119(8)A,α= 95.06(9)°,β= 109.74(10)°,γ= 118.86(10)°,V=705.94A3 Z=1.R=0.086 for 1198 reflections.In the molecule of Ag4(o-CH3C6H4CS2)4 (Py)4 , the cluster core Ag4 has a butterfly configuration, and its coordination situation is similar to that of tetranuclear silver cluster complex Ag4(a-C10H7CS2 )4(Py)4. The molecular configuration of Cu2(o-CH3C6H4CSS2)2(Py)2 is similar to that of Cu2(a-G10H7CSS2)2(Py)2 with Cu-Cu bond of 2.608A. Futhermore, a redox reaction is involved in the reaction between o-methyldithiobenzoic acid and Cu2+. It is also similar to the reaction between a-dithionaphthoic acid and Cu2 + . So o-methyldithiobenzoic acid might be considered to be similar to a-dithionaphthoic acid on steric and electronic effects.