The shortest chalcogen...halogen contacts in molecular crystals

Abstract

The survey of the shortest contacts in structures deposited in the Cambridge Structural Database shows that chalcogen...halogen, halogen...halogen and chalcogen...chalcogen interactions can compete as cohesion forces in molecular crystals. The smallest parameter δ (defined as the interatomic distance minus the sum of relevant van der Waals radii) for Ch...X contacts between chalcogens (Ch: S, Se) and halogens (X: F, Cl, Br, I) is present only in 0.86% out of 30 766 deposited structures containing these atoms. Thus, in less than 1% of these structures can the Ch...X forces be considered as the main type of cohesion forces responsible for the molecular arrangement. Among the 263 structures with the shortest Ch...X contact, there are four crystals where no contacts shorter than the sums of van der Waals radii are present (so-called loose crystals). The smallest δ criterion has been used for distinguishing between the bonding (covalent bond) and non-bonding contacts and for validating the structural models of crystals.