Nonbonded interactions in crystals of halogens and interhalogen compounds

Abstract

We consider a new method of crystal-chemical analysis of intermolecular interactions that employs parameters of atomic Voronoi-Dirichlet polyhedra (VDPs) in the structure as applied to halogens and interhalogen compounds (IHCs). Crystal structure data are used to determine Sm, the surface areas of the VDP faces corresponding to all intermolecular contacts of one molecule in the crystal structure, and Vm, the overall volume of the pyramids whose bases are such faces and the nuclei of atoms involved in intermolecular contacts are in the corners. The enthalpies of sublimation of halogens and the boiling temperatures of halogens and IHCs are linear functions of Sm and Vm, which can be used as scalar descriptors of the 3D structure of molecules.