鼓形有机锡氧杂环羧酸簇合物[PhCH_2Sn(O)(O_2CC_4H_3S)]_6·2CH_2Cl_2 和 [PhCH_2Sn(O)(O_2CC_3H_2NO)]_6·2CH_2Cl_2的合成和晶体结构

Synthesis and Crystal Structure of Drum Organooxotin Clusters from Hetero-aromatic Carboxylic Acid [PhCH_2Sn(O)(O_2CC_4H_3S)]_6·2CH_2Cl_2 and [PhCH_2Sn(O)(O_2CC_3H_2NO)]_6·2CH_2Cl_2

利用三苄基氧化锡与 2 -噻吩甲酸和 2 -唑甲酸反应 ,合成了六聚体苄基锡氧 2 -噻吩甲酸酯 (1 )和六聚体苄基锡氧 2 -唑甲酸酯 (2 )鼓形簇合物 .通过元素分析、红外光谱和 X射线单晶衍射对其结构进行了表征 .测试结果表明 :化合物 1属三斜晶系 ,空间群 P1 ,a=1 . 2 76 0 (3) nm,b=1 .30 5 6 (3) nm,c=1 .334 3(3) nm,α=1 0 5 .6 5 (3)°,β=96 .2 7(3)°,γ=97.2 0 (3)°,Z=1 ,V=2 .0 997(7) nm3 ,Dc=1 .80 9g/ cm3 ,μ=2 .0 97mm- 1 ,F(0 0 0 ) =1 1 1 6 ,R=0 .0 6 5 1 ,w R=0 .1 2 92 .化合物 2属三斜晶系 ,空间群 P1 ,a=1 .2 2 4 0 (4 ) nm,b=1 .36 73(4 ) nm,c=1 .374 4(4 ) nm,α=1 0 7.76 0 (4 )°,β=98.0 6 9(5 )°,γ=91 .4 80(5 )°,Z=2 ,V=2 .1 6 31 (1 2 ) nm3 ,Dc=3.373g/ cm3 ,μ=3.799mm- 1 ,F (0 0 0 ) =2 1 36 ,R=0 .0 382 ,w R=0 .0 79.它们均为鼓形簇状结构 ,锡原子呈畸变的八面体构型 .化合物 1通过分子间 S… S近距离作用 ,形成一维链状结构 .

Two novel drum organooxotin clusters [PhCH 2Sn(O)(O 2CC 4H 3S)] 6·2CH 2Cl 2(1) and [PhCH 2Sn(O)(O 2CC 3H 2NO)] 6·2CH 2Cl 2(2) were synthesized by the reaction of [(PhCH 2) 3Sn] 2O with 2-thiophenecarboxylic acid and 2-oxazoliylcarboxylcarboxylic acid in 1∶2 molar ratio. Their crystal structures were determined by X-ray single crystal diffraction. Crystal 1 belongs to triclinic system with space group P1, a=1.276 0(3) nm, b=1.305 6(3) nm, c=1.334 3(3) nm, α= 105.65(3)°, β=96.27(3)°, γ=97.20(3)°, Z=1, V=2.099 7(7) nm 3, D c=1.809 g/cm 3, μ=2.097 mm -1, F(000)=1 116, R=0.065 1, wR=0.129 2. Crystal 2 belongs to triclinic system with space group P1, a=1.224 0(4) nm, \{b=\}1.367 3(4) nm, c=1.374 4(4) nm, α=107.760(4)°, β=98.069(5)°, γ=91.480(5)°, Z=2, V=2.163 1(12) nm 3, D c=3.373 g/cm 3, μ=3.799 mm -1, F(000)=2 136, R=0.038 2, wR= 0.079. Their structures show a distorted octahedron configuration with six-coordination for the central tin atoms. In crystal 1, the molecules are packed in the unit cell in one-dimensional chain structure through weak interaction between the sulfur atom and one of the sulfur of an adjacent molecule.