Improved Synthesis and X‐Ray Structure of 5‐Aminotetrazolium Nitrate

Abstract

Abstract 5‐Aminotetrazolium nitrate was synthesized in high yield and characterized using Raman and multinuclear NMR spectroscopy ( 1 H, 13 C, 15 N). The molecular structure of 5‐aminotetrazolium nitrate in the crystalline state was determined by X‐ray crystallography: monoclinic, P 2 1 / c, a =1.05493(8) nm, b =0.34556(4) nm, c =1.4606(1) nm, β=90.548(9)°, V =0.53244(8) nm 3 , Z =4, ϱ=1.847 g cm −3 , R 1 =0.034, wR 2 (all data)=0.090. The thermal stability of 5‐aminotetrazolium nitrate was determined using differential scanning calorimetry; the compound decomposes at 167 °C. The enthalpy of combustion (Δ comb H ) of 5‐aminotetrazolium nitrate ([CH 4 N 5 ] + [NO 3 ] − ) was determined experimentally using oxygen bomb calorimetry: Δ comb H ([CH 4 N 5 ] + [NO 3 ] − )=−6020±200 kJ kg −1 . The standard enthalpy of formation (Δ f H °) of [CH 4 N 5 ] + [NO 3 ] − was obtained on the basis of quantum chemical computations at the electron‐correlated ab initio MP2 (second order Møller‐Plesset perturbation theory) level of theory using a correlation consistent double‐zeta basis set (cc‐pVTZ): Δ f H °([CH 4 N 5 ] + [NO 3 ] − (s))=+87 kJ mol −1 =+586 kJ kg −1 . The detonation velocity ( D ) and the detonation pressure ( P ) of 5‐aminotetrazolium nitrate were calculated using the empirical equations by Kamlet and Jacobs: D ([CH 4 N 5 ] + [NO 3 ] − )=8.90 mm μs −1 and P ([CH 4 N 5 ] + [NO 3 ] − )=35.7 GPa.