Structural metrics relationships in covalently bonded organic azides.

Geometrical parameters of covalently bonded organic azides have been analysed using X-ray structural data retrieved from the Cambridge Structural Database. The RNNN fragment geometry shows some important general features: (i) a preference for a trans C(s) configuration; (ii) bending of the N-N-N unit; (iii) substantially different N-N bond lengths in the azide group. Electron-density redistribution within the covalently bonded azide group (relative to that in the isolated azide anion) promotes the capacity of the terminal azide N atom to form hydrogen bonds.