Cocrystals of [1,2,5]oxadiazolo[3,4-c]cinnoline 5-oxides and 1,5-dioxides: step-by-step development of crystal engineering of energetic materials

CrystEngComm. 2025. Vol. 27. No. 3. P. 386–399.

Baraboshkin N. M., Zelenov V. P., Fedyanin I.V., Samigullina A. I., Klenov M. S.

In this work, the cocrystallization of both benzotrifuroxan (BTF) and [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine
4,6-dioxide (furazanotetrazine dioxide, FTDO) with [1,2,5]oxadiazolo[3,4-c]cinnoline 5-oxide (FCO),
1,5-dioxide (FCDO) and some of their nitro derivatives was investigated, focusing on the cocrystal structural
features and their detonation performance. First, cocrystallization energies using crystal structure prediction
(CSP) methods, identifying energetically favorable component ratios for BTF and FTDO with cinnoline
oxides, were calculated. Then two novel cocrystals, the BTF–FCDO 4 (1 : 2) and the FTDO–FCDO 3 (1 : 2)
compositions, were prepared and characterized by X-ray diffraction and Hirshfeld surface analysis. The
primary intermolecular interactions in BTF cocrystals include dominant n(NO2 )⋯π(BTF) contacts and
π-stacking motifs, and in FTDO cocrystals, hydrogen-bonded synthons. The calculated energetic
parameters were 7.37 km s−1 and 23.99 GPa for the FTDO (1 : 2) cocrystal, and 7.69 km s−1 and 26.4 GPa
for the BTF (1 : 2) cocrystal. Their cocrystals (1 : 2) with FCDOs exhibited, compared to pure parent
compounds, lower detonation velocities and pressures due to high FCDOs molar content, yet still
outperformed conventional energetic compounds such as 2,4,6-trinitrotoluene (TNT) and 1,3,5-
trinitrobenzene (TNB).

Keywords: рентгеноструктурный анализ, single crystal X-ray diffraction, crystal structure prediction, инженерия кристаллов, crystal engineering, предсказание кристаллических структур