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

doi:10.1039/C7SC00168A

Powder diffraction and crystal structure prediction identify four new coumarin polymorphs†

Alexander G. Shtukenberg,

*^a Qiang Zhu,

*^bc Damien J. Carter,^d Leslie Vogt,

^e Johannes Hoja,

^fg Elia Schneider,^e Hongxing Song,^e Boaz Pokroy,^h Iryna Polishchuk,^h Alexandre Tkatchenko,

^fg Artem R. Oganov,

^ic Andrew L. Rohl,

^d Mark E. Tuckerman^ejk and Bart Kahr

^al

Author affiliations

* Corresponding authors

^a Department of Chemistry, Molecular Design Institute, New York University, New York City, NY, USA
E-mail: shtukenberg@mail.ru

^b Department of Physics and Astronomy, High Pressure Science and Engineering Center, University of Nevada Las Vegas, Nevada 89154, USA
E-mail: qiang.zhu@unlv.edu

^c Department of Geosciences, Stony Brook University, Stony Brook, NY, USA

^d Curtin Institute for Computation and Department of Chemistry, Curtin University, P.O. Box U1987, Perth, Western Australia, Australia

^e Department of Chemistry, New York University, New York City, NY, USA

^f Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, Berlin, Germany

^g Physics and Materials Science Research Unit, University of Luxembourg, 1511 Luxembourg, Luxembourg

^h Department of Materials Science and Engineering, Russell Berrie Nanotechnology Institute, Technion Israel Institute of Technology, Haifa 32000, Israel

ⁱ Skolkovo Institute of Science and Technology, Skolkovo Innovation Center, 3 Nobel St., Moscow 143026, Russia

^j Courant Institute of Mathematical Sciences, New York University, New York City, NY, USA

^k New York University-East China Normal University Center for Computational Chemistry at NYU Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China

^l Department of Advanced Science and Engineering (TWIns), Waseda University, Wakamatsucho, 3-2, Shinjuku, 162-0056 Tokyo, Japan

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.

$Graphical abstract: Powder diffraction and crystal structure prediction identify four new coumarin polymorphs$

Chemical Science

Powder diffraction and crystal structure prediction identify four new coumarin polymorphs†

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