Geometrical structures of a series of binary azides M(N-3)(n) (M = elements in groups 3 and 13 (n = 3) and in groups 4 and 14 (n = 4)) were investigated at the B3LYP/6-311 +G* level of theory. Our calculations found that binary group 3 triazides M(N-3)(3) (M = Sc, Y, La) and binary group 4 tetraazides M(N-3)(4) (M = Ti, Zr, Hf) turn out to be stable with all frequencies real having a similar linear M-N-NN structural feature, as previously reported for M(N-3)(4) (M = Ti, Zr, Hf). However, binary azides of group 13 M(N-3)(3) (M = B, Al, Ga, In, Tl) and group 14 elements M(N-3)(4) (C, Si, Ge, Sri, Pb) with bent M-N-NN bond angles differ obviously from binary group 3 and 4 azides in geometrical structure. These facts are mainly explained by the difference in electronic density overlap between the central atom and the alpha-N atoms of the azido groups. Two lone-pair electrons on the sp hybridization alpha-N atoms in the binary group 3 and 4 azides donate electron density into two empty d orbitals of the central transition metal atom and a pair of valence bonding electrons, resulting in the alpha-N atoms acting as a tridentate ligand. The sp 2 hybridization alpha-N atoms of the binary group 13 and 14 azides only give one valence electron to form one valence bonding electron pair acting virtually as monodentate donors.