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The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ2 O: O′)bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ2 O: O′)bis[(dimethylformamide-κ O)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two CuII ions are bridged by four syn, syn-η1:η1:μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R22(20) and an R44(36) ring motif formed via O-H...O and O W-H W...O hydrogen bonds. Complex (II) simply packs as molecular species. [ABSTRACT FROM AUTHOR]