二(二异磷酰联硫代磷酸酯)及二(二磷酰联硫代氨基甲酸酯)的合成与结构表征

通过 X-射线衍射 ,确定了化合物二 (二异磷酰联硫代磷酸酯 ) ( [( i Pr O) 2 PS2 ]2 )和二 (二磷酰联硫代氨基甲酸酯 ) ( [Pr2 NCS2 ]2 )的晶体结构。 [( i Pr O) 2 PS2 ]2 是三斜晶系 ,空间群为 P 1 ,晶胞参数为 a=0 .82 99( 2 ) nm,b=0 .8498( 2 ) nm,c=0 .88380 ( 2 ) nm,α=97.98( 3)°,β=1 1 0 .69( 3)°,r=95 .0 1 ( 3)°,Z=2。 [Pr2 NCS2 ]2 是正交晶系 ,空间群 Pbca,点阵参数为 a=1 .1 0 2 32 ( 2 ) nm,b=1 .5 1 645 ( 2 ) nm,c=2 .42 82 6( 1 ) nm,α=β=γ=90°,Z=8。[( i Pr O) 2 PS2 ]2 是中心对称结构 ,两个 P原子和四个 S原子几乎完全处于一个平面上 (原子的最大偏差只有 0 .0 0 4 nm)。在 [Pr2 NCS2 ]2 中 ,两个二硫代氨基甲酸酯基团所在的平面构成的二面角接近 90°,丙基取代的二硫代氨基甲酸酯基团产生扭曲角分别为 2 .9°和 1 .3°。在这两个化合物的结构中 ,联硫基团是通过 S- S单键相连来形成的联硫代化合物。范德华力对晶体结构起到稳定作用

Synthesis and Characterization of the Bis Diisopropylthiophosphate Disulfide and Bis Dipropylthiocarbamoyl Disuffide: [(iPrO)2PS2]2 and [Pr2NCS2]2

The crystal structures of complexes [( i PrO) 2PS 2] 2 and[Pr 2NCS 2] 2 have been determined by X ray crystallography.The former crystallizes in the triclinic system with space group P 1 ,lattice parameters a =0.8299(2)nm, b =0.8498(2)nm, c =0.88380(2)nm, α =97.98(3)°, β =110.69(3)°, r =95.01(3)°,and Z =2.The latter crystallizes in the orthorhombics system with space group Pbca,lattice parometers a =1.10232(2)nm, b =1.51645(2)nm, c =2.42826(1) nm, α=β=γ =90°,and Z =8.The former is a centrosymmetrics structure。The two P atoms and four S atoms are nearly in the same plane, with the maximum deviation 0.004 nm.In the latter,the two dithiocarbamate groups are almost perpendicular to each other,and the torsion angles formed between the propyl groups and dithiocarbamate group are 2.9° and 1.3(3)° respectively.In both structures, the two dithio groups are all bridged by an S S bond forming dissuffide compound.The two crystal structures are all stabilized by van der Waals interactions.