Design and Synthesis of a Series of Nitrogen-Rich Energetic Cocrystals of 5,5′-Dinitro-2H,2H′-3,3′-bi-1,2,4-triazole (DNBT)

Abstract

A series of three energetic cocrystals containing 5,5′-dinitro-2H,2H′-3,3′-bi-1,2,4-triazole (DNBT) were obtained. These incorporate a class of energetic materials that has seen significant synthetic work, the azole family (tetrazoles, triazole, pyrazole, etc.), and yet have struggled to see broad application. A cocrystal was obtained with the triazole 5amino-3-nitro-1H-1,2,4-triazole (ANTA) in a stoichiometry of 2:1 (ANTA:DNBT). Two cocrystals were obtained with the pyrazoles 1H, 4H-3,6-dinitropyrazolo[4,3-c]pyrazole (DNPP) and 3,4-dinitropyrazole (3,4-DNP) in ratios of 1:1 (DNPP:DNBT) and 2:1 (3,4-DNP:DNBT). All three cocrystals, 2:1 ANTA/DNBT (1), 1:1 DNPP/DNBT (2), and 2:1 3,4-DNP/DNBT (3), have high densities (>1.800 g/ cm 3 ) and high predicted detonation velocities (>8000 m/s). In small-scale impact drop tests, cocrystals 1 and 2 were both found to be insensitive, whereas cocrystal 3 possesses sensitivity between that of its two pure components 3,4-DNP and DNBT. The hydrogen bonding motif of the three components with DNBT is preserved among all three cocrystals, and this observation suggests a generally useful motif to be employed in the development of other energetic−energetic cocrystals. These cocrystals represent an area of energetic materials that has yet to be explored for cocrystalline materials.

Synthetic, Crystallographic, and Computational Studies of Extensively Hydrogen Bonded Bilayers in Thermally Stable Adamantane Hydroperoxides

“…Matzger et al. have also identified that the hydrogen‐bond functionality acts as an important interaction in peroxides and energetic materials . The principal binding forces in these crystals are hydrogen bonds.…”

Prediction of the Density of Energetic Co-crystals: a Way to Design High Performance Energetic Materials

“…In other work, by Zhang et al [14], an energetic co-crystal of TNB/NNAP was introduced. A series of nitrogen-rich energetic co-crystals of DNBT was reported by Matzger et al [15]. Landenberger et al [16] have also synthesized some co-crystals of HMX.…”

Detonation Velocity Assessment of Energetic Cocrystals Using QSPR Approach

“…[1][2][3] Recently, a novel technique, known as cocrystallization, provides an elegant method to modify the properties of energetic materials which is also practical in pharmaceutical science. [12] A series of nitrogen-rich energetic cocrystals of DNBT is reported by Matzger et al [13] Landenberger et al have modified the properties of DADP through cocrystallization. The properties of a cocrystal is typically varied from its pure components, in terms of morphology, thermal behavior, sensitivity, detonation performance and so forth.…”