Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

Alexander G. Shtukenberg, Qiang Zhu, Damien J. Carter, Leslie Vogt, Johannes Hoja, Elia Schneider, Hongxing Song, Boaz Pokroy, Iryna Polishchuk, Alexandre Tkatchenko, Artem R. Oganov, Andrew L. Rohl, Mark E. Tuckerman, Bart Kahr

Research output: Contribution to journalArticle

Abstract

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and the need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects.

Original languageEnglish (US)
Pages (from-to)4926-4940
Number of pages15
JournalChemical Science
Volume8
Issue number7
DOIs
StatePublished - 2017

ASJC Scopus subject areas

  • Chemistry(all)

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    Shtukenberg, A. G., Zhu, Q., Carter, D. J., Vogt, L., Hoja, J., Schneider, E., Song, H., Pokroy, B., Polishchuk, I., Tkatchenko, A., Oganov, A. R., Rohl, A. L., Tuckerman, M. E., & Kahr, B. (2017). Powder diffraction and crystal structure prediction identify four new coumarin polymorphs. Chemical Science, 8(7), 4926-4940. https://doi.org/10.1039/c7sc00168a