Johnston Dean H, Agho Ikponmwosa
Department of Chemistry, Otterbein University, Westerville, OH 43081, USA.
Acta Crystallogr E Crystallogr Commun. 2019 Oct 22;75(Pt 11):1705-1711. doi: 10.1107/S205698901901380X. eCollection 2019 Nov 1.
Charge-assisted hydrogen bonding plays a significant role in the crystal structures of solvates of ionic com-pounds, especially when the cation or cations are primary ammonium salts. We report the crystal structures of four ammonium salts of molybdenum halide cluster solvates where we observe significant hydrogen bonding between the solvent molecules and cations. The crystal structures of bis-(anilinium) octa-μ-chlorido-hexa-chlorido--hexa-molybdate ,-di--methyl-formamide tetra-solvate, (CHN)[MoClCl]·4CHNO, (), -phenyl-enedi-ammonium octa-μ-chlorido-hexa-chlorido--hexa-mol-yb-date ,-di-methyl-formamide hexa-solvate, (CHN)[MoClCl]·6CHNO, (), ,'-(1,4-phenyl-ene)bis-(propan-2-iminium) octa-μ-chlorido-hexa-chlo-rido--hexa-molybdate acetone tris-olvate, (CHN)[MoClCl]·3CHO, (), and 1,1'-dimethyl-4,4'-bipyridinium octa-μ-chlo-rido-hexa-chlorido--hexa-molybdate ,-di-methyl-formamide tetra-solvate, (CHN)[MoClCl]·4CHNO, (), are reported and described. In (), the anilinium cations and ,-di-methyl-formamide (DMF) solvent mol-ecules form a cyclic (8) hydrogen-bonded motif centered on a crystallographic inversion center with an additional DMF mol-ecule forming a (2) inter-action. The -phenyl-enedi-ammonium cation in () forms three (2) inter-actions between the three N-H bonds and three independent ,-di-methyl-formamide mol-ecules. The dication in () is a protonated Schiff base solvated by acetone mol-ecules. Compound () contains a methyl viologen dication with ,-di-methyl-formamide mol-ecules forming close contacts with both aromatic and methyl H atoms.
电荷辅助氢键在离子化合物溶剂化物的晶体结构中起着重要作用，尤其是当阳离子为伯铵盐时。我们报道了四种卤化钼簇溶剂化物铵盐的晶体结构，其中我们观察到溶剂分子与阳离子之间存在显著的氢键作用。本文报道并描述了双（苯胺鎓）八 - μ - 氯代 - 六氯代 - μ - 六钼酸盐 - 二 - 二甲基甲酰胺四溶剂化物（(CHN)[MoClCl]·4CHNO）、对苯二铵八 - μ - 氯代 - 六氯代 - μ - 六钼酸盐 - 二 - 二甲基甲酰胺六溶剂化物（(CHN)[MoClCl]·6CHNO）、1,4 - 亚苯基双（丙 - 2 - 亚胺鎓）八 - μ - 氯代 - 六氯代 - μ - 六钼酸盐丙酮三溶剂化物（(CHN)[MoClCl]·3CHO）和1,1'- 二甲基 - 4,4'- 联吡啶鎓八 - μ - 氯代 - 六氯代 - μ - 六钼酸盐 - 二 - 二甲基甲酰胺四溶剂化物（(CHN)[MoClCl]·4CHNO）的晶体结构。在（(CHN)[MoClCl]·4CHNO）中，苯胺鎓阳离子和二甲基甲酰胺（DMF）溶剂分子以一个晶体学反演中心为中心形成一个环状的N-H···O（8）氢键 motif，还有一个额外的DMF分子形成一个C-H···O（2）相互作用。（(CHN)[MoClCl]·6CHNO）中的对苯二铵阳离子在三个N-H键与三个独立的二甲基甲酰胺分子之间形成了三个N-H···O（2）相互作用。（(CHN)[MoClCl]·3CHO）中的双阳离子是一个被丙酮分子溶剂化的质子化席夫碱。化合物（(CHN)[MoClCl]·4CHNO）含有一个甲基紫精双阳离子，二甲基甲酰胺分子与芳香族和甲基H原子都形成了紧密接触。
