An Unusual Layered Crystal Packing Gives Rise to a Superior Thermal Stability of Energetic Salt of 3,6‐Bishydrazino‐1,2,4,5‐tetrazine

Abstract

Five energetic salts of 3,6‐bishydrazino‐1,2,4,5‐tetrazine (BHT), namely (BHT)2(NTO)3 (3), (BHT)(BTT)·2H2O (4), (BHT)(DNP)2 (5), (BHT)(NATr)2 (6), and (BHT)(FOX‐7)2 (7), were synthesized and fully characterized by elemental analysis, FT‐IR, and mass spectra. The crystal structures of salts 3 and 4 were obtained and determined. Sensitivities towards outside stimuli and thermal behaviors of all the compounds were investigated, besides, thermodynamics of both 3 and 4 were calculated as well. The compounds 3–7 exhibit splendid thermal stabilities and satisfactory sensitivities simultaneously. Notably, unlike the previously known layered packing, compound 4 was found to adopt an unusual layered crystal packing with arch layers alternately arranged upward or downward. It may play an important role in contributing to its superior thermal stability (350 °C), providing an enlightening thinking to design new highly thermal stable energetic materials.

Nitroacetonitrile as a versatile precursor in energetic materials synthesis

“…Synthetic transformations which produce multiple energetic functionalities (aka 'explosophore') in a single step are of special interest in the eld. The nitrogen-rich heterocycles including triazoles, 1-7 tetrazole, 1,8-13 triazines, 6,[14][15][16][17] and tetrazines 16,[18][19][20][21][22][23][24][25][26] have found extensive use as the backbone in new energetic materials. Annulated heterocyclic systems are arguably some of the most important backbones; when designing new energetic materials as they oen have some of the most desirable properties including higher thermal stabilities, low sensitivities, and higher densities when compared to the related non-annulated materials; 27,28 however, the syntheses of many annulated heterocyclic systems are complex and consist of many steps (examples shown Schemes 1 and 2).…”