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Two structurally diverse compounds, [Cu(Hbpdc)2(phen)] (1) and [Cu(bpdc)(phen)(H2O)]n (2) (H2bpdc=4,4′-biphenyldicarboxylic acid, phen=1,10-phenanthroline), were synthesized under hydrothermal conditions. Copper atom in 1 is four-coordinated to one bidentate phen ligand and two monodentate partly deprotonated 4,4′-biphenyldicarboxylates. As expected, the structure of 1 is a monomeric species and affords an extended two-dimensional hydrogen bonding architecture. Each copper atom in 2 is five-coordinated to one phen, one water molecule, and two bis-monodentate fully deprotonated 4,4′-biphenyldicarboxylates. Therefore, the structure of 2 is a one-dimensional chain.