A copper(II) complex [Cu(μ-1,3-N 3 )(N 3 )(bpp)] n (1) (bpp=1,3-bis(4′-pyridyl)propane) has been shown to exhibit a two-dimensional network formed by the bpp ligands interlinking copper(II)-azido chains, in which the single azido bridge assumes an asymmetric μ-1,3 mode and mediates weak ferromagnetic coupling. On the other hand, the reaction of cobalt(II), azido and bpp yielded two supramolecular isomers of [Co(N 3 ) 2 (bpp) 2 ] n (2 and 3) in which the azido ions serve as terminal ligands and the metal ions are linked by the bpp ligands in different conformations.