作　　者： ; ; ;

机构地区： 华南师范大学化学与环境学院

出　　处： 《化学通报》 2007年第10期782-786,共5页

摘　　要： 采用X射线衍射法测定二苯并噻吩亚砜单晶结构,发现晶体中二苯并噻吩亚砜分子以反平行三明治式的结构Ⅲ和反平行位移式的结构Ⅳ两种堆砌方式交替堆砌形成有序π-π堆积晶体。二苯并噻吩亚砜单晶结构属于三斜型,空间群为P1,晶体参数为:a=0.84712nm,b=0.94137nm,c=1.20380nm,α=97.866°,β=106.2630°,γ=96.437°,V=0.9014nm3,R1(全部数据)=0.0348和ωR2(全部数据)=0.0814。利用BHandH/6-31+G**方法计算了二苯并噻吩亚砜分子间的π-π堆积作用,Ⅲ和Ⅳ堆砌模式的π-π堆积效应作用能相当大,其计算值分别为-36.06kJ/mol和-39.83kJ/mol,电荷分布表明正负电荷匹配是稳定晶体π-π堆积体系的重要因素。 Crystal structure of dibenzothiophene sulfoxide was obtained by the X-ray diffraction method. It crystallizes in triclinic,space group P ^-1 with a = 0.84712nm, b = 0.94137nm, c = 1.20380nm, α = 97.866°, β = 106.2630°, γ = 96.437°, V = 0.9014nm^3 , R1 （all data） = 0.0348 and ωR2 （all data） = 0.0814. It exhibits a longer S = 0 bond length, which meaning a weak S = 0 bond of dibenzothiophene sulfoxide. With antiparallel-sandwich geometry of Ⅲ and antiparallel-displaced geometry of Ⅳ, the crystals constructed with Ⅲ and Ⅳ alternately following π-π stacking interactions. Theoretical calculations on dibenzothiophene sulfoxide carried out by BHandH method at the 6-31 ＋ G^＊＊ level can give reasonable results for Ⅲ, Ⅳ and Ⅴ structure,furthermore the E π-π,π-π stacking interaction energies,are - 36.06, - 39.83 and - 75.72kJ/mol respectively. The π-π stacking stability of Ⅲ and Ⅳ may be understood by the matching of the charge populations of atoms between two Ⅱ structures.

关 键 词： 二苯并噻吩亚砜 晶体结构 堆积效应

领　　域： [理学] [理学]