Electronic ground state structure and chemistry of nitroguanidine

VESCF(BJ)CI MO reactivity indices were used to provide a consistent rationale for the ground state structure, thermal decomposition and chemistry of nitroguanidine (1). Intra- and inter-molecular NH...O and NH...N hydrogen bonds, attractive and repulsive coulombic forces between nitrogen and oxygen atoms, appear to determine the crystal structure of (1). An intramolecular hydrogen-abstraction reaction and the cleavage of the molecule's weakest bond, viz. (H2N)2C-NNO2, appear to be the main primary thermal decomposition pathways for (1). The nitrimino nitrogen atom and the carbon atom were postulated to be the centres of electrophilic and nucleophilic substitution reactions respectively.