Intermolecular Hydrogen Bonding Directed by Aryl–Perfluoroaryl π–π Stacking Interactions

The crystal structures of five compounds capable of forming self-complementary hydrogen bonds but crystallizing as catemers or creating more complex crystal structures were compared with those of their complexes prepared by cocrystallization with perfluoroaryl compounds. The results of X-ray diffraction revealed that in all the cases, the π–π stacking interactions caused the reorganization of hydrogen bonds and induced the creation of the expected self-complementary hydrogen bond dimeric motifs. The results point to the potential of aryl–perfluoroaryl interactions for the control of molecular self-assembly of aromatic compounds able to form hydrogen bonds. Also, the electrostatic potential (ESP) surfaces were investigated in terms of intermolecular interactions in the studied cocrystals. The values of the locally most negative and most positive ESP confirmed the best donor and acceptor sites for hydrogen bonding and other contacts.