Stabilizing σ-hole Dimethyl Interactions

[Image: see text] Methyl groups bound to electronegative atoms, such as N or O, are recognized to participate in tetrel bonding as Lewis acids. On the other hand, the capability of methyl groups bound to electropositive atoms, such as B or Al, to act as Lewis bases has been recently reported. Herein, we analyze the combination of these two behaviors to establish attractive methyl···methyl interactions. We have explored the Cambridge Structural Database to find experimental examples of these dimethyl-bound systems, finding a significant degree of directionality in the relative disposition of the two methyl groups. Moreover, we have carried out a comprehensive computational analysis at the DFT level of the dimethyl interactions, including the natural bond orbital, energy decomposition analysis, and topological analysis of the electron density (QTAIM and NCI). The dimethyl interaction is characterized as weak yet attractive and based on electrostatics, with a non-negligible contribution from orbital charge transfer and polarization.