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. Peroxide bond: Peroxosolvates of 2‐aminonicotinic acid (I) and lidocaine N‐oxide (II) including unprecedented dodecameric and pentameric discrete hydrogen peroxide clusters were isolated and their structures were determined by single‐crystal X‐ray diffraction. In I and II new double and triple cross‐orientational disorders of H2O2 were found. In II, a hydrogen bond between an H2O2 molecule and a peptide group was observed for the first time.