Different Zeroes of Interaction Energies As the Cause of Opposite Results on the Stabilizing Nature of C–H···O Intramolecular Interactions

The interaction energy of the C–H···O intramolecular interaction is estimated by several methods for a large group of systems possessing a quasi-cyclic six-membered ring. In the case of the geometry corrected method (GCM), the related rotamers method (RRM), and Espinosa’s method (EM), the linear correlations between interaction energies and the electron density at the bond critical point have close slopes. The first and the last two methods yield almost systematically opposite results concerning the stabilizing/destabilizing character of the interaction, and their main difference is their zero of the interaction energy. An investigation on the limitations of reference energies has led to the introduction of the geometry corrected related rotamers method (GCRRM), estimating both stabilizing and destabilizing C–H···O interactions. An extension of EM is proposed.