X-ray structure analysis of the cholesterol 25- and 20-hydroperoxides, the elusive primary sidechain autoxidation products of cholesterol

•The X-ray structure analysis of the primary cholesterol sidechain autoxidation products, cholesterol 25- and 20-hydroperoxides, are presented and analyzed.•Comparison of torsional and bond angles of the sidechain carbons reveal characteristic differences between the conformation of the compounds.•Intermolecular interactions are visualized through Hirshfeld surface analyses and fingerprint plots.•Energy frameworks to calculate intermolecular interaction energies are presented.