Synthesis and Characterization of 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

Abstract

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.

1,2,4‐Triazolium and Tetrazolium Picrate Salts: “On the Way” from Nitroaromatic to Azole‐Based Energetic Materials

“…As can be seen in Figure 8 iodide, [54] azide and perchlorate salts and is analogous to the dinitramide compound.…”

“…In comparison with other azolium salts for which predicted performance data are reported, the azolium picrate salts in this study are predicted to outperform methylated aminotetrazolium salts (6200 m s -1 , 15.5 GPa) [54] and some of them have performances comparable to those of substituted triazolium salts (7500-7900 m s -1 , 20-25 GPa). [54,38,41] A closer look into the heats of formation and detonation parameters ("experimentally determined" or computed) of the azolium picrates studied here clearly illustrates the influence of the cation in these values and allows one to draw conclusions about what sort of cations are best suited for a given application. Compound 1 has a negative heat of formation of -410(30) kJ kg -1 , and substitution of a proton in the ring by a methyl group as in 2 and 3 results in an increase in the exothermicity of the compounds (Ͻ-520 kJ kg -1 ).…”

“…1-Methyl-and 5-amino-2-methyl-1H-tetrazole, [53] 5-amino-1,4-dimethyl-1H-tetrazolium iodide, [54] 5-amino-1,3-dimethyl-1H-tetrazolium iodide, [55] 1,5-diamino-1H-tetrazole, [56] 1,5-diamino-4-methyl-1H-tetrazolium iodide, [18d] guanazine [57] and methylguanazinium iodide [58] were prepared by previously published procedures. In addition, 5-amino-1H-tetrazolium picrate, [19] 1,5-diamino-1H-tetrazolium picrate [20a] and guanazinium picrate [59a] were synthesized by modified literature procedures as indicated below.…”

Preparation, Crystal and Properties of Nitrogen-Rich Energetic Salt of Bis(semicarbazide) 5,5′-Bitetrazole-1,1′-diolate

“…Additionally, the standard enthalpy of the formation of the salt was calculated on the basis of Equations (8) and (9). With the known enthalpies of formation of the carbon dioxide, ∆ f H θ 298 [CO 2 (g)] =´393.5 kJ¨mol´1, and water,…”

“…Recently, much effort has been focused on the research of nitrogen-rich energetic salts with high energetic properties and low sensitivity to impact and friction [5][6][7]. Energetic salts, especially those with excellent performance and environmental compatibility, have been considered as aerospace propellants and explosives [8][9][10][11]. From these salts, azole heterocycles and their derivatives are a unique class due to their high heats of formation, high nitrogen contents, high densities, good thermal stabilities and environmentally benign N 2 as the main reaction product [12][13][14].…”