Supramolecular organization of the organic-inorganic hybrid [{p-(CH3)2NH—C6H4—NH3}2Cl][BiI6]: assembly of a three-dimensional structure via covalent and non-covalent interactions

A new organic-inorganic hybrid [{p-(CH3)2NH—C6H4—NH3}2Cl][BiI6] was synthesized and its crystal structure was established. The hybrid consists of an inorganic anion [BiI6]3− and an organic cation [{p-(CH3)2NH-C6H4-NH3}2Cl]3+. The [BiI6]3− anions are linked via non-covalent I...I interactions between axial atoms of neighboring anions to form chains running along the c axis of the tetragonal unit cell. In the cationic part, the Cl− anion is involved in four (N)H…Cl hydrogen bonds with hydrogen atoms of the p-(CH3)2NH—C6H4—NH32+ cation, forming a two-dimensional substructure. Alternating covalent and I...I halogen bonds in the anionic substructure and cation—anion hydrogen bonds provide the formation of a three-dimensional supramolecular structure with a band gap of 1.93 eV.