Guest-occupiable space in the crystalline solid state: a simple rule-of-thumb for predicting occupancy
Dewald P. van Heerden, Leonard J. Barbour
Abstract
The generally greater degree of thermal motion of guest molecule(s) relative to the host often impedes their accurate modelling in crystal structures. We propose a 'rule-of-thumb' for estimating the maximum number of guest molecules that can be accommodated in a given amount of accessible space in an adequately modelled host structure. A survey of the Cambridge Structural Database was carried out to evaluate the fractional occupancy θ of the accessible space for almost 40 000 solvates involving 20 common solvents. Using widely accessible software tools, the volume of a guest is estimated as its van der Waals surface, while the guest-occupiable space of a potentially porous host is determined as that available to a virtual spherical probe. We propose terminology more appropriate to the supramolecular interpretation of surface typology: the probe-traversable and probe-accessible boundaries as traced out by the locus and surface of a spherical probe, respectively. High-throughput analysis using commercial and free software packages yielded a mean θ = 51.1(4)%, ranging from 45.3(6)% for hexane to 60(1)% for acetic acid.