Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

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 com...

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Main Authors: Shtukenberg, A., Zhu, Q., Carter, Damien, Vogt, L., Hoja, J., Schneider, E., Song, H., Pokroy, B., Polishchuk, I., Tkatchenko, A., Oganov, A., Rohl, Andrew, Tuckerman, M., Kahr, B.
Format: Journal Article
Published: Royal Society of Chemistry Publishing 2017
Online Access:http://purl.org/au-research/grants/arc/DP140101776
http://hdl.handle.net/20.500.11937/54186
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author Shtukenberg, A.
Zhu, Q.
Carter, Damien
Vogt, L.
Hoja, J.
Schneider, E.
Song, H.
Pokroy, B.
Polishchuk, I.
Tkatchenko, A.
Oganov, A.
Rohl, Andrew
Tuckerman, M.
Kahr, B.
author_facet Shtukenberg, A.
Zhu, Q.
Carter, Damien
Vogt, L.
Hoja, J.
Schneider, E.
Song, H.
Pokroy, B.
Polishchuk, I.
Tkatchenko, A.
Oganov, A.
Rohl, Andrew
Tuckerman, M.
Kahr, B.
author_sort Shtukenberg, A.
building Curtin Institutional Repository
collection Online Access
description 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.
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format Journal Article
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institution Curtin University Malaysia
institution_category Local University
last_indexed 2025-11-14T09:57:47Z
publishDate 2017
publisher Royal Society of Chemistry Publishing
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spelling curtin-20.500.11937-541862022-10-12T03:01:42Z Powder diffraction and crystal structure prediction identify four new coumarin polymorphs Shtukenberg, A. Zhu, Q. Carter, Damien Vogt, L. Hoja, J. Schneider, E. Song, H. Pokroy, B. Polishchuk, I. Tkatchenko, A. Oganov, A. Rohl, Andrew Tuckerman, M. Kahr, B. 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. 2017 Journal Article http://hdl.handle.net/20.500.11937/54186 10.1039/c7sc00168a http://purl.org/au-research/grants/arc/DP140101776 http://creativecommons.org/licenses/by/3.0/ Royal Society of Chemistry Publishing fulltext
spellingShingle Shtukenberg, A.
Zhu, Q.
Carter, Damien
Vogt, L.
Hoja, J.
Schneider, E.
Song, H.
Pokroy, B.
Polishchuk, I.
Tkatchenko, A.
Oganov, A.
Rohl, Andrew
Tuckerman, M.
Kahr, B.
Powder diffraction and crystal structure prediction identify four new coumarin polymorphs
title Powder diffraction and crystal structure prediction identify four new coumarin polymorphs
title_full Powder diffraction and crystal structure prediction identify four new coumarin polymorphs
title_fullStr Powder diffraction and crystal structure prediction identify four new coumarin polymorphs
title_full_unstemmed Powder diffraction and crystal structure prediction identify four new coumarin polymorphs
title_short Powder diffraction and crystal structure prediction identify four new coumarin polymorphs
title_sort powder diffraction and crystal structure prediction identify four new coumarin polymorphs
url http://purl.org/au-research/grants/arc/DP140101776
http://hdl.handle.net/20.500.11937/54186