双硫脲-水为主体晶格的四乙基铵包合物的晶体结构及计算

通过单晶X射线衍射法表征了双硫脲-水为主体晶格的四乙基铵包合物(2C_2H_6N_4S_2]~-·2(C_2H_5)_4N]~+·H_2O)的晶体结构,并对双硫脲分子和相应阴离子的空间构型进行了理论计算.结果表明,该包合物属单斜晶系,P2_1/n空间群,晶胞参数a=1.2002(61)nm,b=1.6676(61)nm,c=1.6031(11)nm,β=103.5770(10)°,Z=4,V=3.1192(5)nm~3,R_1=0.0650.包合物中的双硫脲阴离子之间借助多个N-H…S氢键形成二维阴离子氢键主体层,该主体层借助水分子与双硫脲之间存在的O-H…N氢键得以进一步加固,而四乙基铵离子则作为抗衡离子填充在层与层之间,形成了典型的"三明治"夹层包合物结构.双硫脲分子和相应阴离子无论是在晶体结构还是理论计算中都呈现出完全不同的空间构型.

Crystal Structure and Theoretical Calculation of Tetraethylammonium Inclusion Compound with Dithiobiurea and Water Molecules as Anionic Host Lattice

A new inclusion compound of 2C_2H_6N_4S_2]~-·2( C_2H_5)_4N]~+·H_2O was prepared and characterized by X-ray single crystal crystallography. Additionally,the configurations of dithiobiurea and its related anion were discussed with the oretical calculation. Crystal data: monoclinic system,a space group of P2_1/n,a = 1.2002( 61) nm,b = 1.6676( 61) nm,c = 1.6031( 11) nm,β = 103.5770( 10) °,Z = 4,V = 3.1192( 5) nm~3,R_1= 0.0650. By observing the structure,it was found that dithiobiurea anions interacted with each other to generate the host layer structure with the existence of N-H…S hydrogen bonds and the only water molecule further consolidated the anionic layer by O-H…N interactions. Consecutively,the tetraethylammonium cations,as the couterions,were accommodated between the host layers to yield the final typical sandwich-like inclusion compound. Noticeably,the neutral molecule of dithiobiurea and its related anion showed totally different spatial configurations in both the crystal structures and the calculating results.