Nitrogen-rich salts of 3,6-dinitramino-1,2,4,5-tetrazine: syntheses, structures, and energetic properties

Seven energetic salts of 3,6-dinitramino-1,2,4,5-tetrazine (DNAT), named as (NH4)2(DNAT) (1), (NH2NH3)2(DNAT) (2), (NH3OH)2(DNAT) (3), G2(DNAT) (4) (G = guanidine), (AG)2(DNAT) (5) (AG = aminoguanidine), (DAG)2(DNAT)·H2O (6) (DAG = diaminoguanidine) and (TAG)2(DNAT) (7) (TAG = triaminoguanidine) were synthesized and fully characterized. Molecular structures of 1, 4, 6, and 7 were confirmed by single-crystal X-ray diffraction for the first time, which constituted by the nitrogen-rich cations and DNAT2- through electrostatic and H-bond interactions. The thermal behaviors of 1–7 were also investigated, all of these salts have a higher thermal decomposition temperature than DNAT. Enthalpies of formation of these salts were evaluated according to the measurement results of combustion energies, and the detonation performances were calculated via the EXPLO5 v6.01 program. Compound 7 (P: 31.7 GPa, Dv: 9333 m s−1) exhibits the highest detonation performance among them. Sensitivities toward mechanical stimuli of 1–7 were tested by using BAM standard methods, 4 is insensitive to impact and frication (IF>40 J, FS>360 N). Moreover, the relationship between the sensitivity and intermolecular interactions were analyzed by using Hirshfeld surfaces calculations. All studies demonstrated the salts for potential energetic materials.