A series of new Ru(II) half-sandwich complexes with the general formula [(arene)Ru(L)Cl₂], where L is a monodentate amine ligand and arene is a p-cymene or benzene ring, were synthesized and characterized and their supramolecular structures were analyzed. The crystal packing of these compounds was studied using geometrical analysis, Hirshfeld surface analysis and theoretical calculations. Our study reveals the importance of three common hydrogen bonding motifs as the primary factor controlling the supramolecular architecture of this series of complexes. Furthermore, the role of an amine ligand substituent could be different depending on the type of interactions that occurs between functional groups. Interestingly, homomeric self-complementary intermolecular interactions are formed when the ancillary ligand contains benzyl cyanide or alkyl 4-aminobenzoate. These non-conventional interactions could be promising for the design of organometallic supramolecular arrays.