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The Cambridge Structural Database has been used to investigate the detailed environment of H2O2 molecules and hydrogen-bond patterns within "true" peroxosolvates in which the H2O2 molecules do not interact directly with the metal atoms. A study of 65 crystal structures and over 260 hydrogen bonds reveals that H2O2 always forms two H-bonds as proton donors and up to four H-bonds as a proton acceptor, but the latter can be absent altogether. The necessary features of peroxosolvate coformers are clarified. (1) Coformers should not participate in redox reactions with H2O2 and should not catalyze its decomposition. (2) Coformers should be Brønsted bases or exhibit amphoteric properties. The efficiency of the proposed criteria for peroxosolvate formation is illustrated by the synthesis and characterization of several new crystals. Conditions preventing the H2O2/H2O isomorphous substitution are essential for peroxosolvate stability: (1) Every H2O2 in the peroxosolvate has to participate in five or six hydrogen bonds. (2) The distance between the two proton acceptors forming H-bonds with the H2O2 molecule should be longer than the distance defined by the nature of the acceptor atoms. A study of 65 crystal structures and over 260 hydrogen bonds reveals that H2O2 always forms two H-bonds as proton donors and up to four H-bonds as a proton acceptor, but the latter can be absent altogether. [ABSTRACT FROM AUTHOR]

The lattice energy Elattof the two-componentcrystals (three co-crystals, a salt, and a hydrate) is evaluated usingtwo schemes. The first one is based on the total energy of the crystaland its components computed using the solid-state density functionaltheory method with the plane-wave basis set. The second approach exploresintermolecular energies estimated using the bond critical point parametersobtained from the Bader analysis of crystalline electron density orthe pairwise potentials. The Elattvaluesof two-component crystals are found to be lower or equal to the sumof the absolute sublimation enthalpies of the pure components. Thecomputed energies of the supramolecular synthons vary from ∼80to ∼30 kJ/mol and decrease in the following order: acid–amide> acid–pyridine > hydroxyl–acid > amide–amide> hydroxyl–pyridine. The contributions from different typesof noncovalent interactions to the Elattvalue are analyzed. We found that at least 50% of the lattice energycomes from the heterosynthon and a few relatively strong H-bonds betweenthe heterodimer and the adjacent molecules. [ABSTRACT FROM AUTHOR]