Charge distribution as a tool to investigate structural details. II. Extension to hydrogen bonds, distorted and hetero-ligand polyhedra

Abstract

It is shown that one of the main reasons for most failures of the methods for calculating distance-dependent bond strengths is related to the distortion of the coordination polyhedra. The charge distribution (CD) method which depends on only one universal empirical parameter (contraction parameter) is modified to include: (i) an iterative calculation of the effective coordination number (ECoN), to deal with structures containing very distorted coordination polyhedra; (ii) a specific contraction parameter to treat structures containing any type of hydrogen bond; (iii) scale factors for coordination subshells, to treat structures with hetero-ligand polyhedra. The contraction parameter for the hydrogen bonds was obtained from 119 well refined structures based on neutron diffraction data. Examples of the application of the iterative charge distribution (CD-IT) are presented to show the efficiency of the new method in dealing with distorted (including hydrogen bonding) and hetero-ligand polyhedra. In particular, analysis of a series of 74 structures with pentacoordinated cations shows that deviations from overall trends are related to structure instability. The possible failure of the method with polyionic structures and `dynamic' structures is discussed.