Hydrogen Bond Patterns of Dipyridone and Bis(Hydroxypyridinium) Cations

Dipyridonyl-substituted derivatives 2–4 of benzene, pyridine, and pyrazine, respectively, were synthesized to examine the ability of 2-pyridone and its protonated species to direct the self-assembly by hydrogen bonding. Structural analysis by single-crystal X-ray diffraction (SCXRD) of 2 and 4 in trifluoroacetic acid demonstrated that salts are formed as a result of the transfer of protons from the acid to the base (organic species) to generate a bis(hydroxypyridinium) dication. However, if no proton transfer takes place like in the case of crystals of 3 grown from DMSO/H₂O, the self-assembly is mainly directed by the typical R₂²(8) hydrogen bond motif of 2-pyridone. These results indicate that the process of converting a neutral 2-pyridonyl group into a hydroxypyridinium cation makes structure prediction difficult. Consequently, examination of proton transfer and assembly of dipyridone and its protonated species are of interest. In combination with SCXRD, Hirshfeld surface analysis (HSA) was also used to have a better understanding on the nature of intermolecular interactions within crystal structures of 2–4. The large number of F···H/H···F, H···O/O···H, H···H, and H···C/C···H contacts revealed by HSA indicates that hydrogen bonding and van der Waals interactions mainly contribute to crystal packing.