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 (H2 O2 )12 assembly was never observed for small-molecule clusters. In I and II new double and triple cross-orientational disorders of H2 O2 were found. Cluster II is the first example of a peroxosolvate crystal structure containing H2 O2 molecules with a homoleptic hydrogen peroxide environment. In II, a hydrogen bond between an H2 O2 molecule and a peptide group -CONH⋅⋅⋅O2 H2 was observed for the first time.