Van der Waals (vdW) radii (RvdW) are one of the cornerstones of contemporary chemistry. The visual perception and basic analysis of chemical structures and architectures are rooted in the concept of vdW radii providing the basic definition of the atomic "sizes". Even though this concept has a little physical grounding, it is easily interpretable and therefore is widely used in the theoretical chemistry, particularly in design of force fields (in the Lennard-Jones parameter form), dispersion corrections, and COSMO-RS-type solvate models. These models are directly or indirectly operate by the intermolecular interatomic distances, which are regarded as corresponding to the minimum energy of atom-atom interactions and are usually defined as a function of the sum of vdW radii. However, it has been noted that the sum of RvdW for available vdW sets including the most widely used one tabulated by Bondi consistently underestimate the position of the energy minimum by as much as 0.3-0.4 Å. An illustrative example is the C2Cl6 crystal with the shortest r(Cl•••Cl) = 3.65 Å that exceeds significantly the 2RvdW Bondi (Cl) = 3.50 Å. The latter can only be achieved at a very high pressure of ca. 1.2 GPa. Moreover, about 2.0 % (>4 000) of unique organic molecular crystals in the Cambridge Structural Database (CSD) do not contain intermolecular contacts shorter than sum of RvdW (see the first section of SI for the details). The question arises: why are all bonds in these crystals longer than the distance, which is usually considered as the most probable, in other words closest to the energy minimum of the respective interatomic potential?