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Title: Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

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.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5];  [4];  [4];  [6];  [6]; ORCiD logo [5]; ORCiD logo [7]; ORCiD logo [3];  [8]; ORCiD logo [9]
  1. New York Univ. (NYU), NY (United States). Department of Chemistry, Molecular Design Institute
  2. Univ. of Nevada, Las Vegas, NV (United States). Department of Physics and Astronomy, High Pressure Science and Engineering Center; Stony Brook Univ., NY (United States). Department of Geosciences
  3. Curtin University, Perth (Australia). Curtin Institute for Computation and Department of Chemistry
  4. New York Univ. (NYU), NY (United States). Department of Chemistry
  5. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany); University of Luxembourg (Luxembourg). Physics and Materials Science Research Unit
  6. Technion Israel Institute of Technology, Haifa (Israel). Department of Materials Science and Engineering, Russell Berrie Nanotechnology Institute
  7. Skolkovo Institute of Science and Technology, Skolkovo Innovation Center, Moscow (Russia); Stony Brook Univ., NY (United States). Department of Geosciences
  8. New York Univ. (NYU), NY (United States). Department of Chemistry and Courant Institute of Mathematical Sciences; New York University-East China Normal University Center for Computational Chemistry at NYU Shanghai (China)
  9. New York Univ. (NYU), NY (United States). Department of Chemistry, Molecular Design Institute; Waseda Univ., Shinjuku (Japan). Department of Advanced Science and Engineering (TWIns)
Publication Date:
Research Org.:
Board of Regents Nevada System of Higher Education, Las Vegas, NV (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1426142
Grant/Contract Number:  
NA0001982; AC02-98CH10086
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 7; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Shtukenberg, Alexander G., Zhu, Qiang, Carter, Damien J., Vogt, Leslie, Hoja, Johannes, Schneider, Elia, Song, Hongxing, Pokroy, Boaz, Polishchuk, Iryna, Tkatchenko, Alexandre, Oganov, Artem R., Rohl, Andrew L., Tuckerman, Mark E., and Kahr, Bart. Powder diffraction and crystal structure prediction identify four new coumarin polymorphs. United States: N. p., 2017. Web. doi:10.1039/c7sc00168a.
Shtukenberg, Alexander G., Zhu, Qiang, Carter, Damien J., Vogt, Leslie, Hoja, Johannes, Schneider, Elia, Song, Hongxing, Pokroy, Boaz, Polishchuk, Iryna, Tkatchenko, Alexandre, Oganov, Artem R., Rohl, Andrew L., Tuckerman, Mark E., & Kahr, Bart. Powder diffraction and crystal structure prediction identify four new coumarin polymorphs. United States. doi:10.1039/c7sc00168a.
Shtukenberg, Alexander G., Zhu, Qiang, Carter, Damien J., Vogt, Leslie, Hoja, Johannes, Schneider, Elia, Song, Hongxing, Pokroy, Boaz, Polishchuk, Iryna, Tkatchenko, Alexandre, Oganov, Artem R., Rohl, Andrew L., Tuckerman, Mark E., and Kahr, Bart. Mon . "Powder diffraction and crystal structure prediction identify four new coumarin polymorphs". United States. doi:10.1039/c7sc00168a. https://www.osti.gov/servlets/purl/1426142.
@article{osti_1426142,
title = {Powder diffraction and crystal structure prediction identify four new coumarin polymorphs},
author = {Shtukenberg, Alexander G. and Zhu, Qiang and Carter, Damien J. and Vogt, Leslie and Hoja, Johannes and Schneider, Elia and Song, Hongxing and Pokroy, Boaz and Polishchuk, Iryna and Tkatchenko, Alexandre and Oganov, Artem R. and Rohl, Andrew L. and Tuckerman, Mark E. and Kahr, Bart},
abstractNote = {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.},
doi = {10.1039/c7sc00168a},
journal = {Chemical Science},
number = 7,
volume = 8,
place = {United States},
year = {Mon May 15 00:00:00 EDT 2017},
month = {Mon May 15 00:00:00 EDT 2017}
}

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