The compound [Ni(N-3)(2)(bipy)(2)].H2O (I) (bipy=2,2'-bipyridine) has been sunthesized and its structure determined at room temperature. The coordination polyhedron of the Ni atom shows an octahedral topology with the two bipy and the two azido ligands in a cis arrangement. Two monomeric units form an outer-sphere dimer through hydrogen bonding with the water molecule to give the overall formula [Ni(bipy)(2)(N-3)(2)](2).2H(2)O.