A New Nitrogen-Rich Energetic Material with So Many Tautomers

: A new nitrogen-rich triazolo-triazole compound, (3-(6-methyl-1H-[1,2,4]-triazolo-[4,3-b]-[1,2,4]-triazol-3-yl)-1H-1,2,4-triazol-5-amine), TTT1, has been prepared, and its acid-base and tautomeric behavior has been investigated. In the pH range of 0.3-12, TTT1 can accept up to two protons, forming a monocation and a dication, and can deliver one proton, forming a monoanion. The tautomeric behavior is particularly rich for the monocation, for which computational analysis predicts four different tautomers in a narrow energy range of 2 kcal/mol. Two of these tautomers (2H-7H-8H and 3H-7H-8H) have been isolated in salts of the monocation with suitable counterions (chloride, bromide, perchlorate). Surprisingly, the most stable predicted tautomer, 1H-3H-7H, has not been found in the four crystallized salts of the monocation. The energetic perchlorate salt of the monocation (3H-7H-8H tautomer) shows good thermal stability and good stability to impact, friction, and electric discharge. The packing of this compound shows the formation of H-bonded dimers with interactions between N8-H···N1. The crystal structure of this energetic salt was studied experimentally up to 2.8 GPa; no phase change or decomposition was observed.