Increasing the strength and number of hydrogen bonds of azoles and expanding the π–π stacking area are the key factors to improve the thermal stability, which provides a valuable way for developing energetic materials with higher energy and thermal stability.

The synthesis of 5-nitro-2-nitratomethyl-1,2,3,4-tetrazole (4) and its full characterization are given here. Compound 4 was synthesized through the nitration of 5-nitro-2-hydroxymethyl-tetrazole (3) with fuming nitric acid and acetic anhydride and its structure was characterized by MS, FT-IR, ¹H-NMR and ¹³C-NMR techniques. The crystal structure of 4 was determined by X-ray single crystal diffraction analysis. The compound belongs to the orthorhombic system with space group Pna2(1), and its crystal parameters were a = 2.121(8) nm, b = 0.5281(19) nm, c = 0.6246(2) nm, Z = 4, V = 0.6995(4) nm³, Dc = 1.805 g/cm³, F(000) = 384, μ = 0.174 mm⁻¹. A theoretical study of 4 has been performed, using quantum computational density functional theory (B3LYP methods) with 6-31G* basis sets as implemented in the Gaussian 03 program suite. The obtained heat of formation (HOF) for 4 was 228.07 kJ·mol⁻¹, the detonation pressure (P) values calculated for 4 was 37.92 GPa, the detonation velocity (D) can reach 9260 m·s⁻¹, and the oxygen balance was zero (Q), making 4 a competitive energetic compound.