Synthesis, Crystal Structure, and Characterization of Energetic Salts Based on 3,5-Diamino-4H-Pyrazol-4-One Oxime

Abstract

In order to broaden the study of energetic cations, a cation 3,5-diamino-4H-pyrazol-4-one oxime (DAPO) with good thermal stability was proposed, and its three salts were synthesized by a simple and efficient method. The structures of the three salts were verified by infrared spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray diffraction. The thermal stabilities of the three salts were verified by differential scanning calorimetry and thermos-gravimetric analysis. DAPO-based energetic salts are analysed using a variety of theoretical techniques, such as 2D fingerprint, Hirshfeld surface, and non-covalent interaction. Among them, the energy properties of perchlorate (DAPOP) and picrate (DAPOT) were determined by EXPLO5 program combined with the measured density and enthalpy of formation. These compounds have high density, acceptable detonation performance, good thermal stability, and satisfactory sensitivity. The intermolecular interactions of the four compounds were studied by Hirshfeld surface and non-covalent interactions, indicating that hydrogen bonds and π–π stacking interactions are the reasons for the extracellular properties of perchlorate (DAPOP) and picrate (DAPOT), indicating that DAPO is an optional nitrogen-rich cation for the design and synthesis of novel energetic materials with excellent properties.

Interaction of Nitrogen-Rich Cations with Azotriazolone Anions through Ion Exchange Results in the Formation of Energetically Stable and Insensitive Compounds

“…To verify the effect of energetic salt formation on the molecular interaction force of azotriazolone, it is characterized by Hirschfeld surface analysis and 2D fingerprint regions. , From Figure , it can be seen that azoTO 2– maintains a platelike structure in all salts, with distinct red dots on the surface, indicating abundant hydrogen bonding . The 2D fingerprints allow the observation that O···H and N···H are the main intermolecular interactions, and it is noteworthy that the proportion of hydrogen bonding is greater in all of the formed nitrogen-rich salts than in the neutral compound 1 (48.2%).…”

The combined effect of pyrazole and amino groups: preparation of novel energetic coordination compounds with high ClO4− content

“…[3][4][5] Specifically, unlike tetrazole and tetrazine, the pyrazole ring can be protonated to prepare ionic salts due to its basicity, which has been developed by many researchers. [6][7][8] It is precisely because of the special characteristic that even if its derivative groups contain [H + ] which is easily ionizable, it can still be prepared into an ionic salt, such as DAPOP (3,5-diamino-4H-pyrazol-4-one oxime perchlorate salt) 9 (shown in Scheme 1, Path 1a). In addition, even if pyrazole forms multiple fused rings with tetrazine or triazole, this characteristic remains unchanged because the binding site for [H + ] is still on the pyrazole skeleton, such as DATTP (3,6diamino-1,2,4-triazolo [4,3-b]tetrazine perchlorate salt) and FTP ( [1,2,4]triazolo[4′,3′:1,5]- [1,2,4]triazolo [3,4-f] [1,2,4]triazolo [1,5-d] [1,2,4]triazine-2,5,10-triamine perchlorate salt) 10,11 (shown in Scheme 1, Path 1b and 1c).…”