Hydrogen Peroxide Insular Dodecameric and Pentameric Clusters in Peroxosolvate Structures

Peroxosolvates of 2‐aminonicotinic acid ( I ) and lidocaine N ‐oxide ( II ) including the largest insular hydrogen peroxide clusters were isolated and their crystal structures were determined by single‐crystal X‐ray diffraction. An unprecedented dodecameric hydrogen peroxide insular cluster was found in I . An unusual cross‐like pentameric cluster was observed in the structure of II . The topology of the (H₂O₂)₁₂ assembly was never observed for small‐molecule clusters. In I and II new double and triple cross‐orientational disorders of H₂O₂ were found. Cluster II is the first example of a peroxosolvate crystal structure containing H₂O₂ molecules with a homoleptic hydrogen peroxide environment. In II , a hydrogen bond between an H₂O₂ molecule and a peptide group ‐CONH⋅⋅⋅O₂H₂ was observed for the first time.