From Hydrate to Peroxosolvate: A Test of Prediction with Cyclic N ‑Oxides

Peroxosolvate formation is a promising method for developing energetic materials with improved properties (e.g., oxygen balance and overall performance); however, one challenge that remains is the prediction of compounds that are likely to form peroxosolvates. Hydrogen bond donation in hydrate structures was exploited to identify possible hydrogen peroxide solvate formers in the Cambridge Structural Database, leading to the discovery of a peroxosolvate crystal form for each of the six N -oxide compounds that met the search criteria. The resulting peroxosolvates were characterized by single-crystal X-ray diffraction and Raman spectroscopy, and the crystal structures were compared with the corresponding hydrate structures to identify trends in hydrogen bond donation, demonstrating that, in the developed peroxosolvates, the O–H···O–N interaction is stronger in the peroxosolvate than in the hydrate. The success of this peroxosolvate discovery strategy for N -oxide-containing compounds provides insight into how to identify target molecules that may form peroxosolvates; this study will affect energetic materials in particular, where the compounds can be dangerous to handle and/or difficult to synthesize.