Robust motifs in 2-phenylethylammonium and related tetrahalometallates

The novel crystal structures of seven compounds which combine 2-phenylethylammonium cations and perhalometallate anions, all with the general formula (C8H9NH3+)2 MX42-, were determined to establish the effect of metal atom and halogen ligand substitution on the structures and hydrogen bonding interactions. Five of the structures, bis(2-phenylethylammonium) tetrachlorozincate, (C8H9NH3+)2 ZnCl42-, bis(2-phenylethylammonium) tetraiodozincate, (C8H9NH3+)2 ZnI42-, bis(2-phenylethylammonium) tetrabromodichloroiodozincate, (C8H9NH3+)2 ZnCl2BrI2-, bis(2-phenylethylammonium) tetrabromocadmate, (C8H9NH3+)2 CdBr42-, and bis(2-phenylethylammonium) tetrabromomercurate, (C8H9NH3+)2 HgBr42-, were found to be isostructural, while two of the compounds containing iodo ligands, bis(2-phenylethylammonium) tetraiodocadmate, (C8H9NH3+)2 CdI42-, and bis(2-phenylethylammonium) tetraiodomercurate, (C8H9NH3+)2 HgI42-, crystallize in a different, but related disordered structure. Strong N+-HX--M hydrogen bonding interactions, as well as weaker C-H[small pi] aromatic interactions occur in all seven structures, and two robust tetrameric hydrogen bonded zero-dimensional motifs are present in all seven structures. C-HCl-M hydrogen bonding interactions are present in the structure of bis(2-phenylethylammonium) tetrachlorozincate, and result in the distortion of the geometry of the 2-phenylethylammonium cation. Comparison of the identified zero-dimensional hydrogen bonding motifs with those occurring in related structures reported in the literature shows that the motifs are robust and can tolerate changes in cation, metal and ligand to a large extent.