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作为系统研究大环硫氮杂冠醚结构的一部分,合成了1,4,10,13-四硫-7,16-二氮杂环十八冠醚的硝酸盐[H_2(C_(12)H_(26)N_2S_4)(NO_3)_2]1和镍配合物[Ni(C_(12)H_(26)N_2S_4)Cl_2·4H_2O]2,并测定和计算了它们的晶体结构和电子结构.化合物1属单斜晶系,空间群 P2_1/c,a=7.936(5),b=8.866(7),c=14.756(5),β=95.33(4)°,V=1033.7~3,Z=2,D_o=1.45g·cm~(-3),μ=43.7cm~(-1),F(000)=480,最终偏离因子 R=0.059,R_w=0.059.化合物2属三斜晶系,空间群 PI,a=6.941(4),b=9.862(3),c=16.507(3)(?),α=98.78(2),β=95.52(3),γ=93.48(3)°,V=1108.3~3,Z=2,D_o=1.58g·cm~(-3),μ=14.9cm~(-1),F=(000)=556,最终偏离因子 R=0.060,R_w=0.065.晶体结构测定结果表明:化合物1与自由配体 L 相比较,N 原子的构型变化最大,在氯化镍配合物2中,四硫二氮大环发生严重扭曲,其中四个 S 和两个 N 原子在 Ni 原子周围形成八面体配位,Ni—N 距离从2.109到2.140(?),Ni—S 距离从2.370到2.435.同时,量化计算结果说明,S、N 原子与 Ni~(2+)配位时均为电子授体,且 S 对 Ni~(2+)的授电子能力,似略大于 N 原子.
As part of systematic study of the structure of macrocyclic thiazene crown ether, the nitrate of [H_2 (C_ (12) H_ (26) N_2S_4) (NO_3) _2] 1 and Ni (C_ (12) H_ (26) N_2S_4) Cl_2 · 4H_2O] 2 were synthesized and their crystal structures and electronic structures were determined and calculated. Monoclinic, space group P2_1 / c, a = 7.936 (5), b = 8.866 (7), c = 14.756 (5), β = 95.33 (4) °, V = 1033.7-3, Z = D_o = 1.45g · cm -3, μ = 43.7cm -1, F (000) = 480, final deviation factor R = 0.059, R_w = 0.059. Compound 2 is a triclinic system with space group PI = a = 6.941 (4) b = 9.862 (3) c = 16.507 (3) ?,? = 98.78 (2),? = 95.52 (3),? = 93.48 1108.3-3, Z = 2, D_o = 1.58g · cm -3, μ = 14.9cm -1, F = (000) = 556, the final deviation factor R = 0.060, R_w = 0.065. The results of structure determination show that the configuration change of N atom is the largest when compound 1 is compared with that of the free ligand L, and the tetrathiazepine ring is seriously distorted in the nickel chloride complex 2, in which four S and two N The atoms formed octahedral coordination around Ni atom, the distance of Ni-N was from 2.109 to 2.140 (?), And the distance of Ni-S from 2.370 to 2.435. At the same time, Both S and N atoms are electron-donor when coordinated with Ni 2+, and S has a slightly larger electron-donor ability than Ni atom.