Ion-molecular Crystals as Inclusion Compounds: Van der Waals Contacts in Ionic Carbonates

Abstract

Among Cambridge substances, which always include “organic”carbon, i.e., carbon contained in molecules or molecular ions,ion-molecular crystals (particularly, carbonates or alkaline-earthand alkaline metals) are of special interest. Some of such carbonatescontain pronounced Van der Waals (vdw) contacts between oxygenatoms of carbonate groups. Thus, agglomerates (layers or columns)formed by contacting carbonate groups arise (columns beingconnected in a frame), and in the cavities between these agglomeratescations are situated. The structure looks like an inclusion compound,the carbonate groups being hosts and the cations being guests. Todiscuss this question we used the refined value of vdw radius of oxygenwhich was obtained by statistical treatment of 8200 crystal structuresfrom Cambridge Structural Database (CSD) and is equal to 1.53 A for the O⋯O contacts. Hence the length of a normal supporting vdw contact O⋯O is 3.06 ± 0.15 A. Such contacts are present in MgCO3 and CaCO3 (calcite) and in α-Na2CO3. There are contacts O⋯O that are even shorter (2.74–2.81 A)in CaCO3 (aragonite), SrCO3, BaCO3 and Li2CO3.So it is possible to suppose the existence of specific (partly covalent)contacts O⋯O in these substances. In β-Na2CO3, all forms of K2CO3, Rb2CO3 and Cs2CO3 the vdw contacts of CO3 groups are absent; therefore they are ionic (not inclusion) compounds.