Combined X-ray Crystallographic and Periodic DFT Study of Supramolecular Organization and Intermolecular Interactions in Crystalline Peroxosolvates of (Nitropyrazolyl)furazans

Combined X-ray Crystallographic and Periodic DFT Study of Supramolecular Organization and Intermolecular Interactions in Crystalline Peroxosolvates of (Nitropyrazolyl)furazans Full article

Journal

Crystal Growth & Design
ISSN: 1528-7483 , E-ISSN: 1528-7505

Output data

Year: 2025, Volume: 25, Number: 5, Pages: 1394-1405 Pages count : 12 DOI: 10.1021/acs.cgd.4c01396

Authors

Medvedev Alexander G. ¹ , Prikhodchenko Petr V. ¹ , Dalinger Igor L. ² , Vener Mikhail V. ¹ , Churakov Andrei V. ¹

Affiliations

1	N.S.Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Prosp. 31, 119991 Moscow, Russia
2	N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii Prosp. 47, 119991 Moscow, Russia

Hydrogen peroxide is a source of active oxygen, which can optimize the negative oxygen balance of energy compounds and improve their detonation properties due to the formation of crystalline peroxosolvates. This approach has been recently proposed but remains unexplored because the number of hydrogen peroxide adducts and energetic compounds is very limited. Due to its acidic nature, hydrogen peroxide usually forms stable peroxosolvates with basic or amphoteric coformers. Herein, peroxosolvates of amphoteric energetic compounds, (nitropyrazolyl)furazanes C6H5N5O3·H2O2 (1·H2O2), C6H4N6O5·H2O2 (2·H2O2), and 5(C5H2N6O5)·H2O2 (3·1/5H2O2), were obtained, and their crystal structures were determined. Crystal packings of 1–3 are based on the same supramolecular synthon formed by a peroxide molecule and three adjacent coformers. In this unit, H2O2 forms three hydrogen bonds: one with the furazan ring as the proton donor and two with pyrazolyl fragments as both a proton donor and a proton acceptor. Analysis of the metric parameters of H-bonds in previously published isostructural crystalline hydrates 1·H2O and 2·H2O indicates the predominant acidic nature of amphoteric coformers. Periodic density functional theory (DFT) calculations reveal that the total sum of hydrogen bonds as a proton donor of the hydrogen peroxide molecule is up to 10 kJ mol–1 higher than the hydrogen bond energy as a proton acceptor, reflecting the acidic nature of H2O2. The contribution of hydrogen bonds of hydrogen peroxide molecules to the lattice energy of the resulting peroxosolvates is about 40–45%. 1·H2O2 exhibits improved oxygen balance and estimated detonation parameters in comparison to unsolvated 1, whose structure was also determined.

Medvedev A.G. , Prikhodchenko P.V. , Dalinger I.L. , Vener M.V. , Churakov A.V.
Combined X-ray Crystallographic and Periodic DFT Study of Supramolecular Organization and Intermolecular Interactions in Crystalline Peroxosolvates of (Nitropyrazolyl)furazans
Crystal Growth & Design. 2025. V.25. N5. P.1394-1405. DOI: 10.1021/acs.cgd.4c01396 WOS OpenAlex

Web of science:	WOS:001432869300001
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