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.
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- cluster compounds
- hydrogen bonds
- hydrogen peroxides
- structure elucidation
- supramolecular chemistry