In this manuscript we combine high level ab initio calculations (RI-MP2/aug-cc-pVTZ) and the analysis of several crystal structures to demonstrate the existence of π-hole aerogen bonding interactions in Xe(IV) compounds. The ability of XeF4 and Xe(OMe)4 to interact with electron rich molecules is rationalized using several computational tools, including molecular electrostatic potential surfaces, energetic and geometric features of the complexes and “atoms in molecules” (AIM) and Natural Bond Orbital (NBO) analyses. We have found support for the π-hole interaction involving the xenon atom from the solid state architecture of several X-ray structures retrieved from the crystal structural depot. Particularly, π-hole aerogen bonding interactions are quite common in the solid state of Xe(IV) compounds.
