Polymorphism and Peroxomorphism in Peroxosolvates of Zwitterionic Sulfonic Acids: Features of H-Bonding and Crystal Packing

A novel class of crystalline hydrogen peroxide adducts, peroxosolvates of zwitterionic sulfonic acids C2H7NO3S center dot H2O2 (1), p-C6H7NO3S center dot H2O2 (2), p-C6H7NO3S center dot 0.5(H2O2) (3), m-C6H7NO3S center dot H2O2 (4), o-C6H7NO3S center dot H2O2 (5), C5H5NO3S center dot H2O2 (6), C12H8N2O3S center dot H2O2 (7), C8H17NO3S center dot 2(H2O2) (8), C10H9NO4S center dot 1.25(H2O2)center dot 0.25(H2O) (9), C10H9NO4S center dot H2O2 (10), and C10H9NO4S center dot 0.94(H2O2)center dot 0.06(H2O) (11), were prepared from highly concentrated hydrogen peroxide, and their structures were determined by X-ray crystallography. In all compounds, first observed charge-assisted HOOH center dot center dot center dot-O3S- and well-known NH+center dot center dot center dot-O3S- hydrogen bonds played a predominant role in crystal packing. The influence of H-bonding on valent S-O distances was discovered. A comparative analysis of the HOOH center dot center dot center dot O hydrogen bond strength was performed. Polymorphism and temperature-induced phase transition for organic peroxosolvates were observed for the first time. A noticeable temperature dependence of hydrogen peroxide O-O distance was found for compound 8.

Automated summary

A novel class of crystalline hydrogen peroxide adducts was prepared and their structures were determined by X-ray crystallography. The study found that hydrogen bonding plays a predominant role in crystal packing and influences valent S-O distances. A comparative analysis of the HOOH center dot center dot center dot O hydrogen bond strength was performed.