Synthesis of group 15-triazides E(N(3))(3) (E = Sb 1, Bi 2) and Py(2)-Bi(N(3))(3)3 (Py = pyridine). Single crystals of 1 were in situ grown by an IR-laser-assisted technique on the diffractometer. The structure of 3, which represents the first structurally characterized neutral Bi-triazide, is influenced by crystal packing effects according to DFT calculations.