The structures of 1 and 2 consist of layers ofcopper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4′-bpy (1) ligands and terminalmonodentate 2,4′-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08×4.99 Å2, theedges being defined by the Phmal and 4,4′-bpy ligands. The intralayer copper−copper separations in 1 throughthe anti−syn equatorial−apical carboxylate-bridge and the 4,4′-bpy molecule are 4.9922(4) and 11.083(1) Å,respectively.