Isolation of a Moderately Stable but Sensitive Zwitterionic Diazonium Tetrazolyl-1,2,3-triazolate

Abstract

An unexpected formation of a diazonium compound was observed by nitration of an amino substituted triazolyl tetrazole with mixed acid. The crystal structure determination revealed a zwitterionic diazonium tetrazolyl-1,2,3-triazolate, whose constitution was supported by NMR and vibrational spectroscopic analysis. The thermal stability and sensitivity toward impact and friction were determined. In contrast, diazotriazoles are rather unstable and are mainly handled in solution and/or low temperatures, which is not the case for this diazonium tetrazolyl-1,2,3-triazolate, being stable at ambient temperature.

High Density Energetic Zwitterionic Diazonium 1,2,4‐Triazolate Resulting from an Interesting Bond Cleavage of E‐1,2‐Bis(3,4‐diamino‐1,2,4‐triazol‐5‐yl)‐ethane

“…Additionally, the triazole ring and the diazo group are considered to be approximately in the plane, which can be illustrated from the N2–N3–C1–N4 torsion angle of −177.40(18)° and the C2–N1–C1–N4 torsion angle of 177.19(19)°. The diazonium bond N4–N5 bond length of 1.095(2) Å is in the range of normal N≡N triple bond, which is almost equal to those of other previously reported diazonium inner salts (1.088(2) Å, 1.096(3) Å, 1.111(2) Å and 1.112(2) Å). Moreover, the diazonium group is coplanar with 1,2,4‐triazolate which can also attribute to one σ covalent bond and two π covalent bonds in the N≡N triple bond, comparing with non‐coplanar azido groups in 1,2,4‐triazole substituted polynitro‐benzene and 1,2,3‐triazole dendrictic esters .…”

Aminonitro Groups Surrounding a Fused Pyrazolotriazine Ring: A Superior Thermally Stable and Insensitive Energetic Material

“…The continuing successful development of high energy density materials (HEDMs) is indispensable on the way to high-performance and insensitive molecules. − In addition, increasing thermal stability appears to be a prime goal in the evolution of next-generation HEDMs, especially in the field of heat-resistant explosives. − Relying on nitrobenzene, traditional heat-resistant explosives always show excellent thermal stability and low pressure encountered in space applications, but they have a low detonation performance and have to face many environmental issues during the process of manufacture. − In recent years, nitrogen-rich heterocylic compounds have appeared to be ideal candidates for the preparation of novel heat-resistant explosives. Some of them do show high thermal stabilities with good detonation performance; however, their thermal decomposition temperatures are always lower than 300 °C, − which is still a big challenge that needs to be addressed for applications in this field.…”

Gem‐dinitromethyl‐substituted Energetic Metal–Organic Framework based on 1,2,3‐Triazole from in situ Controllable Synthesis

“…Compound 5 crystallizes in the orthorhombic space group Pn ma with four molecular moieties in the unit cell and ad ensity of 1.729 gcm À3 at 293 K. Compound 6·H 2 O crystallizes in the monoclinic space group P2 1 /c with ad ensity of 2.145 gcm À3 at 130 K. Compound 8 crystallizes in the orthorhombics pace group Pn nm with eight molecular moieties in the unit cell and ad ensity of 2.040 gcm À3 at 296 K. Duringn itrationo rn ucleophilic substitution reactions, H-proton usually transferred from 2-substitutedp ositiont o1-or 3-substituted positions, which have been reported recently. [14,15] In this work, H-proton transfers in compound 5 and 6 but settles in the 2substituted positiono fc ompound 8,w hich may attribute to the symmetry of two gem-dinitromethyl groups. In com-Scheme2.Synthesis of derivatives 4-8 based on 3 with or without trifluoroacetic acid as ac atalyst and different solution effects in the reduction by iodine potassium.…”

“…Their crystal structures and crystal packing were shown in Figure – and the crystallographic data and refinement details, selected bond lengths, angles are given in Table S2–12. Compound 5 crystallizes in the orthorhombic space group P nma with four molecular moieties in the unit cell and a density of 1.729 g cm −3 at 293 K. Compound 6⋅H 2 O crystallizes in the monoclinic space group P 2 1 / c with a density of 2.145 g cm −3 at 130 K. Compound 8 crystallizes in the orthorhombic space group P nnm with eight molecular moieties in the unit cell and a density of 2.040 g cm −3 at 296 K. During nitration or nucleophilic substitution reactions, H‐proton usually transferred from 2‐substituted position to 1‐ or 3‐ substituted positions, which have been reported recently . In this work, H‐proton transfers in compound 5 and 6 but settles in the 2‐substituted position of compound 8 , which may attribute to the symmetry of two gem ‐dinitromethyl groups.…”