1,4-Dimethyl-5-aminotetrazolium 5-nitrotetrazolate (2) was synthesized in high yield from 1,4-dimethyl-5-aminotetrazolium iodide (1) and silver 5-nitrotetrazolate. Both new compounds (1, 2) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy ( 1 H, 13 C, 14 N, 15 N), elemental analysis and single crystal X-ray diffraction. 1,4-Dimethyl-5aminotetrazolium 5-nitrotetrazolate (2) represents the first example of an energetic material which contains both a tetrazole based cation and anion. Compound 2 is hydrolytically stable with a high melting point of 190 8C (decomposition). The impact sensitivity of compound 2 is very low (30 J), it is not sensitive towards friction (> 360 N).The molecular structure of 1,4-dimethyl-5-aminotetrazolium iodide (1) in the crystalline state was determined by X-ray crystallography: orthorhombic, F ddd , a ¼ 1.3718(1) nm, b ¼ 1.4486(1) nm, c ¼ 1.6281(1) nm, V ¼ 3.2354(5) nm 3 , Z ¼ 16, 1 ¼ 1.979 g cm À1 , R 1 ¼ 0.0169 (F > 4s(F)), wR 2 (all data) ¼ 0.0352.The molecular structure of 1,4-dimethyl-5-aminotetrazolium 5nitrotetrazolate (2) in the crystalline state was also determined by X-ray crystallography: orthorhombic, P 2 1 2 1 2 1 , a ¼ 0.5709(1) nm, b ¼ 1.2866(2) nm, c ¼ 1.3328(2) nm, V ¼ 0.9789(3) nm 3 , Z ¼ 4, 1 ¼ 1.548 g cm À1 , R 1 ¼ 0.0389 (F > 4s (F)), wR 2 (all data) ¼ 0.0973.

Ionic salts containing the novel 5-amino-2-methyl-and 5-amino-1,3-dimethyltetrazolium cations with energetic anions (perchlorate, nitrate, azide and dinitramide) have been synthesized in high yields and purities and fully characterized. A full structural description by spectroscopic methods (vibrational and 15 N NMR spectroscopy) and X-ray analysis is given. Unexpectedly, salts based on the asymmetric 5-amino-1,3-dimethyltetrazolium cation have higher densities than analogue compounds containing the isomeric 5-amino-1,4-

There are great demands to develop explosives with higher performance accompanied by reduced sensitivities towards external stimuli, higher thermal stability and improved environmental acceptability. This contribution presents modified nitramines, which were investigated by nucleophilic substitution reactions of potassium salts of 5‐amino‐3‐nitro‐1,2,4‐triazole, 3,5‐dinitro‐1,2,4‐triazole, 3,5‐dinitroimidazole, 2,4‐dinitroimidazole, 4‐amino‐3,5‐dinitropyrazole, 3,5‐dinitropyrazole, 3,4‐dinitropyrazole and 3,4,5‐trinitropyrazole on 1,3‐dichloro‐2‐nitrazapropane. The energetic compounds were comprehensively characterized and their detonation parameters were calculated by the EXPLO5 code. Heats of formation were calculated by the atomization method using CBS‐4M electronic enthalpies. The presented compounds show detonation performances comparable to pentaerythritol tetranitrate (PETN). In addition, they possess high thermal stabilities and low sensitivities, which make them interesting for further investigations and possible applications as insensitive, high‐energy dense materials.

Ammonium‐dinitroguanidine (ADNQ) and 1,7‐diamino‐1,7‐dinitrimino‐2,4,6‐trinitro‐2,4,6‐triazaheptane (APX) have been synthesized in high yield and purity. Both compounds were characterized by multinuclear NMR (1H, 13C, 14N) and vibrational spectroscopy. The molecular structures were elucidated by single‐crystal X‐ray diffraction. ADNQ crystallizes in the monoclinic space group P21/c with a crystal density of ρ = 1.735 g·cm–3, APX in the orthorhombic space group Pbnc with a crystal density of ρ = 1.911 g·cm–3. ADNQ decomposes at 197 °C, APX at 174 °C. Impact (IS), friction (FS) and electrostatic discharge (ESD) sensitivities were determined experimentally for both compounds. (ADNQ: IS ≥ 10 J, FS ≥ 252 N and ESD ≥ 0.4 J, APX: IS ≥ 3 J, FS ≥ 80 N and ESD ≥ 0.1 J). Polymer bonded mixtures of APX with 5 % PVAA resin proved to be less sensitive towards mechanical stimuli (IS ≥ 5J, FS = 160 N). The detonation parameters (EXPLO5 code) were calculated using combined quantum chemical (CBS‐4M) methods and a chemical equilibrium calculation based on the steady‐state model of detonation: ADNQ (Vdet = 9066 m·s–1, pC–J = 332 kbar, Qv = –5193 kJ·kg–1), APX (Vdet = 9540 m·s–1, pC–J = 395 kbar, Qv = –5935 kJ·kg–1). The experimentally determined detonation velocity (fibre optic technique) agrees well with the theoretical values, indicating that APX shows better detonation performance than HMX (1,3,5,7‐Tetranitro‐1,3,5,7‐tetraazoctane).

Combination of the nitramine 1-chloro-2-nitrazapropane and nitro-substituted azoles yielded energetic materials for potential use as TNT replacements in melt-cast formulations.