The Polymorphs of ROY: A Computational Study of Lattice Energies and Conformational Energy Differences*
Sajesh P. Thomas A and Mark A. Spackman A B
+ Author Affiliations
- Author Affiliations
A School of Molecular Sciences, University of Western Australia, Perth, WA 6009, Australia.
B Corresponding author. Email: mark.spackman@uwa.edu.au
Australian Journal of Chemistry 71(4) 279-284 https://doi.org/10.1071/CH17620
Submitted: 30 November 2017 Accepted: 11 January 2018 Published: 8 February 2018
Abstract
The remarkable structural diversity observed in polymorphs of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (commonly known as ROY) challenges computational attempts to predict or rationalize their relative stability. This modest study explores the applicability of CE-B3LYP model energy calculation of lattice energies (using experimental crystal structures), supplemented by a systematic approach to account for conformational energy differences. The CE-B3LYP model provides sensible estimates of absolute and relative lattice energies for the polymorphs, provided care is taken to achieve convergence in the summation of pairwise terms. Conformational energy differences based on density functional theory (DFT) energies are shown to be unreliable, but MP2 energies based on DFT-optimized structures show considerable promise.
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