Packing of Planar Organic Molecules: Interplay of van der Waals and Electrostatic Interaction

The molecular packing motifs occurring in the crystal structures of pentacene and its two oxo-derivatives (6,13-pentacenequinone and 5,7,12,14-pentacenetetrone) have been analyzed. Both oxygen containing species exhibit an almost coplanar stacking while pentacene adopts a face-on-edge herringbone packing. The different packing motifs are well explained by quantum chemical ab initio calculations of the electronic structure of the molecular entities exhibiting a pronounced charge localization at the oxygen atoms of both oxo-derivatives which causes an additional electrostatic O-π interaction favoring a planar stacking. Moreover, the polarizability of the π-system is reduced and the molecular quadrupole moment is altered, both resulting in a decrease of the lattice energy of the oxo-species as evidenced by the sublimation energy obtained for all three species from thermal desorption measurements. This emphasizes the importance of the balance between electrostatic and van der Waals interactions for the packing in molecular crystals.