Jump to main content
Jump to site search

Issue 2, 2021
Previous Article Next Article

Guest-occupiable space in the crystalline solid state: a simple rule-of-thumb for predicting occupancy

Author affiliations

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.

Graphical abstract: Guest-occupiable space in the crystalline solid state: a simple rule-of-thumb for predicting occupancy

Back to tab navigation

Supplementary files

Article information


Submitted
12 Aug 2020
First published
09 Dec 2020

Chem. Soc. Rev., 2021,50, 735-749
Article type
Tutorial Review

Guest-occupiable space in the crystalline solid state: a simple rule-of-thumb for predicting occupancy

D. P. van Heerden and L. J. Barbour, Chem. Soc. Rev., 2021, 50, 735
DOI: 10.1039/D0CS01040E

Social activity

Search articles by author

Spotlight

Advertisements