Charge assisted assembly of zwitterionic pyridone hydrates

Abstract Two pyridone derivatives, bearing the pyridinium moiety (1), or dimethylpyridinium moiety (2), have been synthesized and their crystal structures have been determined. The compounds crystalize in hydrated zwitterionic forms with either two (1•2H2O) or four (2•4H2O) water molecules. The zwitterionic networks contain different types of water clusters, generated into channels, incorporating them into the network by sandwiching. The type of channel depends on the crystal lattice and the nature of non-covalent interactions established between zwitterions as well as the number of water molecules incorporated into the architecture. 1 affords tubes filled in with water channels formed by water tetramers, contrary to 2, which affords a layered network altering the zwitterionic layer and the layer formed by water tetramers and hexamers. A detailed study of intermolecular interactions of both crystal structures and a quantification of interaction energies has been performed using PIXEL lattice energy calculations, giving an insight to a quantitative evaluation of interactions through Coulombic, disperse, repulsion and polarization energies. The strongest pairwise, in both structures, is found to be a dipole–dipole interaction between oppositely charged heterocyclic rings. The differences in the crystal packings of these hydrates have been elucidated by the fingerplot analysis. The comparative studies between experimental and calculated (DFT) data of molecules 1•2H2O and 2•4H2O for systems of different complexity are performed. Furthermore, correlations of experimental and calculated bond lengths and the simulation of compound solvation with the CPCM model are done.