Three new polynuclear compounds based on a dicarboxylic acid ligand are reported. In particular, two Cu(II) coordination compounds, [Cu 2 (H 2 O) 6 (Hbzlidp) 2 ](CF 3 SO 3 ) 2 ·2H 2 O ( 1 ) and [Cu(NO 3 )(Hbzlidp)] ∞ ( 2 ) (bzlidp 2− = N -benzyliminodipropionate anion), and a Ni(II) dinuclear compound, [Ni 2 (H 2 O) 4 (bzlidp) 2 ] ( 3 ), were synthesized and characterized by IR spectroscopy, elemental analysis and single crystal X-ray diffraction. Different structures were obtained depending on the reaction conditions. The structural analyses reveal that 1 was formed by dinuclear [Cu 2 (H 2 O) 6 (Hbzlidp) 2 ] 2+ units built by two copper(II) ions joined through two Hbzlidp − ligands, while 2 was formed by pairs of Cu(II) centers bridged by four syn , syn carboxylate groups to generate “paddle wheel” units. The dinuclear copper units are arranged in a rhombus type grid, in a 2-D layer structure. In both cases, the N was protonated and not coordinated to the metal center. Compound 3 was formed by [Ni 2 (H 2 O) 4 (bzlidp) 2 ] neutral dinuclear units, with octahedral Ni(II) centers. Solution studies of the ligand–M(II) systems (M(II) = Mn, Co, Ni, Cu, Zn, Cd, and Pb) were also carried out.