Comparative Study of Weak Interactions in Molecular Crystals:  H−H Bonds vs Hydrogen Bonds

The crystal structures of tetraphenylphosphonium squarate, bianthrone, and bis(benzophenone)azine are shown to contain a variety of C−Hδ+···δ+H−C interactions, as well as a variety of C−H···O and C−H···Cπ interactions. Each of these molecules possesses interactions that can possibly be characterized as either H−H bonds or weak hydrogen bonds based on the first four criteria proposed by Koch and Popelier. These interactions have been completely characterized topologically after the multipole refinement of the structures. It appears that weak interactions of the form C−Hδ+···δ+H−C possess certain correlations between the various properties of the electron density at the bond critical points. The coexistence of the three types of interactions makes it possible to establish similarities and differences in the correlations of these weak interactions. This all leads to a better understanding of H−H interactions and how they fit into the hierarchy of weak interactions.