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Dynamics and disorder: on the stability of pyrazinamide polymorphs

This article focuses on the structure and relative stability of four pyrazinamide polymorphs. New single crystal X-ray diffraction data collected for all forms at 10 K and 122 K are presented. By combining periodic ab initio DFT calculations with normal-mode refinement against X-ray diffraction data...

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Autores principales: Hoser, Anna Agnieszka, Rekis, Toms, Madsen, Anders Østergaard
Formato: Online Artículo Texto
Lenguaje:English
Publicado: International Union of Crystallography 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9254588/
https://www.ncbi.nlm.nih.gov/pubmed/35695115
http://dx.doi.org/10.1107/S2052520622004577
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author Hoser, Anna Agnieszka
Rekis, Toms
Madsen, Anders Østergaard
author_facet Hoser, Anna Agnieszka
Rekis, Toms
Madsen, Anders Østergaard
author_sort Hoser, Anna Agnieszka
collection PubMed
description This article focuses on the structure and relative stability of four pyrazinamide polymorphs. New single crystal X-ray diffraction data collected for all forms at 10 K and 122 K are presented. By combining periodic ab initio DFT calculations with normal-mode refinement against X-ray diffraction data, both enthalpic and entropic contributions to the free energy of all polymorphs are calculated. On the basis of the estimated free energies, the stability order of the polymorphs as a function of temperature and the corresponding solid state phase transition temperatures are anticipated. It can be concluded that the α and γ forms have higher vibrational entropy than that of the β and δ forms and therefore they are significantly more stabilized at higher temperatures. Due to the entropy which arises from the disorder in γ form, it overcomes form α and is the most stable form at temperatures above ∼500 K. Our findings are in qualitative agreement with the experimental calorimetry results.
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spelling pubmed-92545882022-07-14 Dynamics and disorder: on the stability of pyrazinamide polymorphs Hoser, Anna Agnieszka Rekis, Toms Madsen, Anders Østergaard Acta Crystallogr B Struct Sci Cryst Eng Mater Hans-Beat Bürgi tribute This article focuses on the structure and relative stability of four pyrazinamide polymorphs. New single crystal X-ray diffraction data collected for all forms at 10 K and 122 K are presented. By combining periodic ab initio DFT calculations with normal-mode refinement against X-ray diffraction data, both enthalpic and entropic contributions to the free energy of all polymorphs are calculated. On the basis of the estimated free energies, the stability order of the polymorphs as a function of temperature and the corresponding solid state phase transition temperatures are anticipated. It can be concluded that the α and γ forms have higher vibrational entropy than that of the β and δ forms and therefore they are significantly more stabilized at higher temperatures. Due to the entropy which arises from the disorder in γ form, it overcomes form α and is the most stable form at temperatures above ∼500 K. Our findings are in qualitative agreement with the experimental calorimetry results. International Union of Crystallography 2022-06-01 /pmc/articles/PMC9254588/ /pubmed/35695115 http://dx.doi.org/10.1107/S2052520622004577 Text en © A. A. Hoser et al. 2022 https://creativecommons.org/licenses/by/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
spellingShingle Hans-Beat Bürgi tribute
Hoser, Anna Agnieszka
Rekis, Toms
Madsen, Anders Østergaard
Dynamics and disorder: on the stability of pyrazinamide polymorphs
title Dynamics and disorder: on the stability of pyrazinamide polymorphs
title_full Dynamics and disorder: on the stability of pyrazinamide polymorphs
title_fullStr Dynamics and disorder: on the stability of pyrazinamide polymorphs
title_full_unstemmed Dynamics and disorder: on the stability of pyrazinamide polymorphs
title_short Dynamics and disorder: on the stability of pyrazinamide polymorphs
title_sort dynamics and disorder: on the stability of pyrazinamide polymorphs
topic Hans-Beat Bürgi tribute
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9254588/
https://www.ncbi.nlm.nih.gov/pubmed/35695115
http://dx.doi.org/10.1107/S2052520622004577
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