The 4,4'-bipyridine-based zwitterionic monocarboxylate ligand, 4,4'-dipyridinio-1 -acetate (L), is used as coligand to construct novel magnetic coordination polymers with mixed azide and carboxylate bridges. Two compounds, [Co-2(L)(2)(N-3)(4)(H2O)]center dot 4H(2)O (1) and [Mn-6(L)(4)(N-3)(12)(H2O)]center dot 5H(2)O (2), have been structurally and magnetically characterized. Compound 1 consists of one-dimensional (1D) coordination chains in which the unprecedented binuclear motifs with mixed (mu-EO-N-3)(mu-COO)(2) (EO = end-on) triple bridges are cross-linked by the 4,4'-dipyridinium-N-methylene spacers. In compound 2, the azide anions link the metal ions into a very complicated three-dimensional (3D) network with unprecedented topology, and the zwitterionic coligand is embedded in and serves as additional supports for the 3D network. Magnetic studies reveal that the mixed (mu-EO-N-3)(mu-COO)(2) triple bridges transmit ferromagnetic coupling in the Co(II) compound, and the overall antiferromagnetic interactions exist in the Mn(II) compound.