Crystals of the highly energetic material bis(3,4-diamino-1,2,4-triazolium) dinitramide (2) representing one of the thermally most stable dinitramide derivatives which is due to the insertion of the long disregarded bis(3,4-diamino-1,2,4-triazolium) cation.
Received (in XXX, XXX) Xth xxx 201x, Accepted Xth XXXXXXXXX 201xDOI: xx.xxx/b000000x 5 4,4',5,5'-Tetraamino-3,3'-bi-1,2,4-triazole (1) was prepared in one step from commonly available starting materials. Compound 1 comprises two combined aromatic triazoles with four amino moieties resulting in a compound which has i) a high temperature stability, ii) a high heat of formation, iii) high density and iv) no sensitivity towards physical stimuli (friction, impact and electrostatic discharge). Interestingly the compound has never been considered as building block in the development of new energetic materials. Therefore 1 was investigated in detail as a potential new nitrogen-rich, temperature stable cation for synthesis of energetic ionic derivatives (2−13) as 10 environmentally benign explosives. The cation was combined mostly with oxygen-rich counter-anions such as dinitramide (2), 5nitrotetrazole-2-oxide (3), 5-nitrotetrazolate (4), nitrate (5), tetranitrobisimidazole (6), 5,5'-bitetrazole-1,1'-dioxide (7), 1,1'-dinitramino-5,5'-bitetrazolate (8), 5-nitriminotetrazolate (9), 1-methyl-5-nitriminotetrazolate (10), perchlorate (11), picrate (12), nitroformate (13). Compounds 2-10 and 13 were characterized by low temperature single-crystal X-ray diffraction. All compounds were investigated by NMR and vibrational (IR, Raman) spectroscopy, mass spectrometry and elemental analysis. The excellent thermal properties were 15 determined by differential thermal analysis (DTA). The sensitivities towards impact, friction, and electrical discharge were investigated using BAM standards and a small scale electrostatic discharge tester. The detonation parameters of those compounds without inclusion of crystal water (1-3, 5-8, 11 and 13) were calculated using the EXPLO5 (V6.02) code and calculated (CBS-4M) enthalpy of formation values. + ). They 65 strongly vary in their stability towards temperature and in their energetic performance. A common observed trend in simple nitrogen-rich cations is the decrease in temperature stability in the