Stereochemical effect of lone pair electrons of chlorine atoms in the ClO3- and ClO2- anions

Crystal-chemical analysis of 2035 crystal structures containing perchlorate , chlorate, or chlorite ions is carried out. The Voronoi-Dirichlet (VD) pol yhedra make it possible to quantitatively characterize the influence of a l one pair of electrons (E pair) on the specific features of the Cl(V) and Cl (III) coordination spheres. In the ClO3E- and ClO2E2- ions, the chlorine at oms are displaced from the barycenters of their VD polyhedra by 0.55(11) an d 0.50(3) Angstrom, respectively. The chlorine atoms of the ClO4- ions are located roughly at the barycenters of their VD polyhedra. The volume of the E pair localized at the chlorine atoms in ClO3- and ClO2- ranges from 5.3 to 7.0 Angstrom(3).