Rademeyer, MelanieTsouris, ChristosBilling, David G.Lemmerer, AndreasCharmant, Jonathan2011-08-082011-08-082011-02-21Rademeyer, M, Tsouris, C, Billing, DG, Lemmerer, A & Charmant, J 2011, 'Robust motifs in 2-phenylethylammonium and related tetrahalometallates', CrystEngComm, vol. 13, pp. 3485–3497.1466-803310.1039/c0ce00634chttp://hdl.handle.net/2263/17019The novel crystal structures of seven compounds which combine 2-phenylethylammonium cations and perhalometallate anions, all with the general formula (C8H9NH3 +)2 MX4 2 , 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 ZnCl4 2 , bis(2-phenylethylammonium) tetraiodozincate, (C8H9NH3 +)2 ZnI4 2 , bis(2- phenylethylammonium) tetrabromodichloroiodozincate, (C8H9NH3 +)2 ZnCl2BrI2 , bis(2- phenylethylammonium) tetrabromocadmate, (C8H9NH3 +)2 CdBr4 2 , and bis(2- phenylethylammonium) tetrabromomercurate, (C8H9NH3 +)2 HgBr4 2 , were found to be isostructural, while two of the compounds containing iodo ligands, bis(2-phenylethylammonium) tetraiodocadmate, (C8H9NH3 +)2 CdI4 2 , and bis(2-phenylethylammonium) tetraiodomercurate, (C8H9NH3 +)2 HgI4 2 , crystallize in a different, but related disordered structure. Strong N+–H/X –M hydrogen bonding interactions, as well as weaker C–H/p aromatic interactions occur in all seven structures, and two robust tetrameric hydrogen bonded zero-dimensional motifs are present in all seven structures. C–H/ Cl–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.en© The Royal Society of Chemistry 2011.Robust motifsTetrahalometallatesHydrogen bondingArticle