Crystal Structure and Improved Synthesis of 1‐(2H‐Tetrazol‐5‐yl)guanidium Nitrate

Energetic derivatives of tetrazoles are one of the key areas of research focus in pursuit of novel high energy materials, useful as propellants and explosives. Herein, the crystal structure and an improved synthetic procedure of 1‐(2H‐tetrazol‐5‐yl)guanidine ( 1 ) and its nitrate salt ( 2 ) are reported. The compounds were structurally characterized by spectroscopic (FT‐IR, ¹H NMR, ¹³C NMR) and elemental analysis. The molecular structure of tetrazolyl guanidium nitrate ( 2 ) was solved using low temperature single‐crystal X‐ray diffraction. 2 crystallized as its hemihydrate in the orthorhombic space group Fdd2, with a crystal density of 1.69 g cm⁻³. Thermal behavior and decomposition of the molecules were studied with differential scanning calorimetry (DSC). Molar enthalpy of formation (Δ_fH^m) of compound 2 was back calculated from heat of combustion (Δ_cH⁰) value obtained experimentally using bomb calorimetric measurements. Lattice enthalpy of 1‐(2H‐tetrazol‐5‐yl)guanidium nitrate was directly calculated from measured crystal density using Jenkins equation. Preliminary ballistic parameters of the compound were predicted and compared with reported high nitrogen tetrazole derivatives.