fac-[Re(CO)₃(2-nben)Cl] and fac-[Re(CO)₃(4-nbzen)Cl] complexes consisting of 2-nbzen = N,N′-bis(2-nitrobenzaldehyde)-1,2-diiminoethane and 4-nbzen = N,N′-bis(4-nitrobenzaldehyde)-1,2-diiminoethane were synthesized by the reaction of Re(CO)₅Cl with nbzen ligands. These complexes were characterized by physico-chemical, spectroscopic methods and X-ray crystallography. The electrochemical behavior of the two complexes was investigated by cyclic voltammetry. In the crystal structure of [Re(CO)₃(4-nbzen)Cl], the neighbouring molecules are linked together by intermolecular C–H···Cl interactions to form 1D extended chains along the b-axis.