One hydrogen malonato-bridged complex of formula [Cu(Hmal)2] (1) and two polymorphous malonato-bridged complexes of formula [Cu(H2O)(H2mal)(mal)] (2 and 3), in which the three species of the malonate (H2mal, Hmal−, and mal2−) are present, were synthesised and characterized by X-ray diffraction [H2mal = malonic acid]. Their structures consist of corrugated malonate layers of [Cu(Hmal)2] (1) and [Cu(H2O)(H2mal)(mal)] (2 and 3) units bridged by carboxylate–malonate groups. The layers are linked through hydrogen bonds leading to a three-dimensional network. Variable-temperature (1.9–290 K) magnetic susceptibility measurements indicate the occurrence of weak ferromagnetic interactions between the copper(II) ions through the carboxylate–malonate bridge. The effectiveness of magnetic exchange coupling is related to the degree of protonation of the malonate group.
