Cupric oxide is one of the most important additives used (a) to catalyze decomposition reactions in gas generators to obtain cooler reaction gases, (b) as burning enhancer for ammonium perch lorate-based composite propellants, and (c) as coloring agent in pyrotechnics. In this context, the reaction of Cu2+ ions in aqueous ammonia solution with bis(tetrazolyl)amine (H(2)bta) was investigated. Depending on the reaction conditions three complexes were obtained: Cu(bta)(NH3)(2) (1), Cu(bta)(NH3)(2).H2O (2), and (NH4)(2)Cu(bta)(2)(.)2.5H(2)O (3). The crystal structures of 1 and 2 are discussed with respect to the coordination mode of the dianion of N,N-bis(1(2)H-tetrazol-5-yl)-amine (bta), which mediates in the case of 1 and 2 weak superexchange interactions between the adjacent magnetic transition-metal Cu-II cations. These antiferromagnetic interactions result from 1D copper chains over an hidden azide end-to-end bridge. Interestingly, the structural arrangement of 1 completely changes in the presence of crystal-bound water. Moreover, some physicochemical properties (e.g., heat of formation, friction, and impact sensitivity, DSC) of these complexes with respect to high-energetic materials are discussed.