LAUSR

Abstract Two structurally similar mononuclear vanadium(V) complexes, [VO 2 (L 1 )] ( 1 ) and [VO 2 (L 2 )] ( 2 ) [where HL 1  = 1-(2-(dimethylamino)ethyliminomethyl)naphthalen-2-ol and HL 2  = 1-(2-(diethylamino)ethyliminomethyl)naphthalen-2-ol] have been synthesized and characterized by elemental and spectral analysis. Structures of both complexes have been confirmed by single crystal X-ray diffraction studies. Weak non-covalent interactions lead to the formation of extended supramolecular assemblies in them. The crystal packing in complex 2 is different compared to that in complex 1 due to the presence of ethyl groups instead of methyl groups bonded to the nitrogen atoms in the ligand moieties. The importance of non-covalent C H⋯π, π⋯π (chelate ring) and hydrogen bonding interactions in the solid state of both complexes has been described by means of DFT and MEP calculations and characterized using Bader’s theory of “atoms in molecules” (AIM). Particular attention has been paid to those interactions involving the chelate ring that are referred as uncommon interactions in this manuscript.