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Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/c7sc00168a· OSTI ID:1426142
 [1];  [2];  [3];  [4];  [5];  [4];  [4];  [6];  [6];  [5];  [7];  [3];  [8];  [9]
  1. New York Univ. (NYU), NY (United States). Department of Chemistry, Molecular Design Institute; Department of Chemistry, Molecular Design Institute, New York University, New York City, NY
  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)

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.

Research Organization:
Board of Regents Nevada System of Higher Education, Las Vegas, NV (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0001982
OSTI ID:
1426142
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 7 Vol. 8; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (86)

A New Era for ab initio Molecular Crystal Lattice Energy Prediction journal October 2014
Bernauer′s Bands journal March 2011
Modeling Polymorphic Molecular Crystals with Electronic Structure Theory journal March 2016
First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications journal March 2017
Convergence Properties of Crystal Structure Prediction by Quasi-Random Sampling journal January 2016
Exchange-Hole Dipole Dispersion Model for Accurate Energy Ranking in Molecular Crystal Structure Prediction journal January 2017
Harmonically Assisted Methods for Computing the Free Energy of Classical Crystals by Molecular Simulation: A Comparative Study journal January 2017
How Evolutionary Crystal Structure Prediction Works—and Why journal March 2011
Conformational Polymorphism journal December 2013
Benchmarking Calculated Lattice Parameters and Energies of Molecular Crystals Using van der Waals Density Functionals journal July 2014
Exploring the Lower Limit in Hydrogen Bonds:  Analysis of Weak C−H···O and C−H···π Interactions in Substituted Coumarins from Charge Density Analysis journal February 2005
Seamless and Accurate Modeling of Organic Molecular Materials journal March 2013
Density functional theory including dispersion corrections for intermolecular interactions in a large benchmark set of biologically relevant molecules journal January 2006
Crystal structure prediction using ab initio evolutionary techniques: Principles and applications journal June 2006
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
A benchmark for non-covalent interactions in solids journal August 2012
Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory journal September 2012
Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals journal July 2013
Order-parameter-aided temperature-accelerated sampling for the exploration of crystal polymorphism and solid-liquid phase transitions journal June 2014
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials journal September 2009
Temperature-Accelerated Method for Exploring Polymorphism in Molecular Crystals Based on Free Energy journal June 2011
Anharmonic and Quantum Fluctuations in Molecular Crystals: A First-Principles Study of the Stability of Paracetamol journal September 2016
Generalized Gradient Approximation Made Simple journal October 1996
First-Principles Determination of the Structure of Magnesium Borohydride text January 2012
Van der Waals Density Functional for General Geometries text January 2004
Upack program package for crystal structure prediction: Force fields and crystal structure generation for small carbohydrate molecules journal June 1999
Two-Dimensional X-Ray Diffraction book January 2009
Porous and Dense Magnesium Borohydride Frameworks: Synthesis, Stability, and Reversible Absorption of Guest Species journal September 2011
Many-Body Dispersion Interactions in Molecular Crystal Polymorphism journal May 2013
Porous and Dense Magnesium Borohydride Frameworks: Synthesis, Stability, and Reversible Absorption of Guest Species journal September 2011
Growth Actuated Bending and Twisting of Single Crystals journal January 2014
Many-Body Dispersion Interactions in Molecular Crystal Polymorphism journal May 2013
Accurate description of van der Waals complexes by density functional theory including empirical corrections journal January 2004
First-principles modeling of molecular crystals: structures and stabilities, temperature and pressure: First-principles modeling of molecular crystals
  • Hoja, Johannes; Reilly, Anthony M.; Tkatchenko, Alexandre
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 7, Issue 1 https://doi.org/10.1002/wcms.1294
journal December 2016
Mikroskopische Untersuchungen an polymorphen Substanzen: II. Mitteilung journal March 1939
Zum mikrochemischen Nachweis des Cumarins journal December 1934
Recent advances in magnetic structure determination by neutron powder diffraction journal October 1993
Exploiting multiple levels of parallelism in Molecular Dynamics based calculations via modern techniques and software paradigms on distributed memory computers journal June 2000
A Projector Augmented Wave (PAW) code for electronic structure calculations, Part I: atompaw for generating atom-centered functions journal April 2001
High-throughput crystallization: polymorphs, salts, co-crystals and solvates of pharmaceutical solids journal February 2004
Ab initio molecular simulations with numeric atom-centered orbitals journal November 2009
New developments in evolutionary structure prediction algorithm USPEX journal April 2013
Using experimental studies and theoretical calculations to analyze the molecular mechanism of coumarin, p-hydroxybenzoic acid, and cinnamic acid journal May 2005
Dispersion-Corrected Mean-Field Electronic Structure Methods journal April 2016
Realizing Predicted Crystal Structures at Extreme Conditions:  The Low-Temperature and High-Pressure Crystal Structures of 2-Chlorophenol and 4-Fluorophenol journal May 2005
Hirshfeld Surfaces Identify Inadequacies in Computations of Intermolecular Interactions in Crystals: Pentamorphic 1,8-Dihydroxyanthraquinone journal December 2008
Phase Behavior and Polymorphism of Organic Crystals Confined within Nanoscale Chambers journal November 2009
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids journal January 1996
Resorcinol Crystallization from the Melt: A New Ambient Phase and New “Riddles” journal March 2016
Role of Electrostatic Interactions in Determining the Crystal Structures of Polar Organic Molecules. A Distributed Multipole Study journal January 1996
Transient Resonance Raman and ab Initio MO Calculation Studies of the Structures and Vibrational Assignments of the T 1 State and the Anion Radical of Coumarin and Its Isotopically Substituted Analogues journal January 1997
Quantum dissipation driven by electron transfer within a single molecule investigated with atomic force microscopy journal March 2020
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Fingerprinting intermolecular interactions in molecular crystals journal January 2002
Thermal properties of molecular crystals through dispersion-corrected quasi-harmonic ab initio calculations: the case of urea journal January 2016
Static and lattice vibrational energy differences between polymorphs journal January 2015
Modelling organic crystal structures using distributed multipole and polarizability-based model intermolecular potentials journal January 2010
Crystal-structure prediction of pyridine with four independent molecules journal January 2011
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Projector augmented-wave method journal December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures journal October 2008
Higher-accuracy van der Waals density functional journal August 2010
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data journal February 2009
Temperature-Accelerated Method for Exploring Polymorphism in Molecular Crystals Based on Free Energy journal June 2011
Accurate and Efficient Method for Many-Body van der Waals Interactions journal June 2012
First-Principles Determination of the Structure of Magnesium Borohydride journal December 2012
Role of Dispersion Interactions in the Polymorphism and Entropic Stabilization of the Aspirin Crystal journal July 2014
Anharmonic and Quantum Fluctuations in Molecular Crystals: A First-Principles Study of the Stability of Paracetamol journal September 2016
Generalized Gradient Approximation Made Simple journal October 1996
Van der Waals Density Functional for General Geometries journal June 2004
Materials perspective on Casimir and van der Waals interactions journal November 2016
COMPACK : a program for identifying crystal structure similarity using distances journal January 2005
Constrained evolutionary algorithm for structure prediction of molecular crystals: methodology and applications journal May 2012
Determination of the molecular packing in the crystal of coumarin by means of potential-energy calculations journal May 1974
Why don't we find more polymorphs? journal July 2013
Report on the sixth blind test of organic crystal structure prediction methods
  • Reilly, Anthony M.; Cooper, Richard I.; Adjiman, Claire S.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 4 https://doi.org/10.1107/S2052520616007447
journal August 2016
Exploring polymorphism of benzene and naphthalene with free energy based enhanced molecular dynamics journal August 2016
Organic crystal polymorphism: a benchmark for dispersion-corrected mean-field electronic structure methods journal August 2016
Effect of packing motifs on the energy ranking and electronic properties of putative crystal structures of tricyano-1,4-dithiino[ c ]-isothiazole journal August 2016
Ab initio determination of the crystalline benzene lattice energy to sub-kilojoule/mole accuracy journal August 2014
Monte Carlo indexing with McMaille journal September 2004
Constrained evolutionary algorithm for structure prediction of molecular crystals: methodology and applications text January 2012
A Materials Perspective on Casimir and van der Waals Interactions text January 2015
Anharmonic and Quantum Fluctuations in Molecular Crystals: A First-Principles Study of the Stability of Paracetamol text January 2016
Mbd software March 2016

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Reliable and practical computational description of molecular crystal polymorphs journal January 2019
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GAtor: A First Principles Genetic Algorithm for Molecular Crystal Structure Prediction text January 2018
Polymorphism of l -Tryptophan journal November 2019
A theoretical NMR study of selected benzazoles: Comparison of GIPAW and GIAO-PCM (DMSO) calculations journal November 2017
In situ temperature-modulated microscopy observation of two-phase co-existing states of coumarin and coumarin derivative in melting journal November 2018
Structure prediction drives materials discovery journal April 2019
Computational polymorph screening reveals late-appearing and poorly-soluble form of rotigotine journal June 2019
From serendipity to supramolecular design: assessing the utility of computed crystal form landscapes in inferring the risks of crystal hydration in carboxylic acids journal January 2018
Crystal structure prediction of flexible pharmaceutical-like molecules: density functional tight-binding as an intermediate optimisation method and for free energy estimation journal January 2018
Crystal structure prediction is changing from basic science to applied technology journal January 2018
Towards the systematic crystallisation of molecular ionic cocrystals: insights from computed crystal form landscapes journal January 2018
ROY revisited, again: the eighth solved structure journal January 2018
First-principles stability ranking of molecular crystal polymorphs with the DFT+MBD approach journal January 2018
Evolutionary niching in the GAtor genetic algorithm for molecular crystal structure prediction journal January 2018
Is zeroth order crystal structure prediction (CSP_0) coming to maturity? What should we aim for in an ideal crystal structure prediction code? journal January 2018
Crystal structure prediction: reflections on present status and challenges journal January 2018
Hydrogen bonding vs. stacking interaction in the crystals of the simplest coumarin derivatives: a study from the energetic viewpoint journal January 2019
Theory and practice of modeling van der Waals interactions in electronic-structure calculations journal January 2019
Overcoming the difficulties of predicting conformational polymorph energetics in molecular crystals via correlated wavefunction methods journal January 2020
Discovery of new polymorphs of the tuberculosis drug isoniazid journal January 2020
Endpoint-restricted adiabatic free energy dynamics approach for the exploration of biomolecular conformational equilibria journal August 2018
Towards hybrid density functional calculations of molecular crystals via fragment-based methods journal September 2018
Structure Prediction Drives Materials Discovery text January 2019
Towards Hybrid Density Functional Calculations of Molecular Crystals via Fragment-Based Methods text January 2018


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