Preprint of "BEST-CSP benchmark study of polymorphs I and II of sulfamerazine and the perils of polytype polymorphs"

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Autores principales: Červinka, Ctirad, Bouzek, Karel, Paušová, Šárka
Formato: Recurso digital
Lenguaje:inglés
Publicado: Zenodo 2025
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author Červinka, Ctirad
Bouzek, Karel
Paušová, Šárka
author_facet Červinka, Ctirad
Bouzek, Karel
Paušová, Šárka
contents We report the outcome of an interdisciplinary investigation by the BEST-CSP network of the kinetically favoured form I and the low temperature stable form II of the drug sulfamerazine (SMZ). A new structure determination of form II at 150 K is presented, allowing a better comparison with form I (SLFNMA04). Attempts to find the solvent-mediated transition temperature were complicated by observing that various slurrying experiments produce a new polymorph, sulfamerazine Form V, which is closely related to form I but with an alternative packing of the double layers, i.e. is a polytype polymorph. Forms I and V are only distinguishable by high-quality X-ray diffraction. Form V appears to be marginally more stable than form I above 50 °C. The experimental data, including heat capacities and thermal expansion are used to test a wide range of assumptions and energy models for calculating free energy differences between these, polymorphs, in particular the composite quasi-harmonic approximation, relying on DFT and DFTB quantum-chemical theories. This work illustrates the challenges in computational the thermodynamic transition temperature between form I and II. The complications caused by the discovery of form V are discussed.
format Recurso digital
id zenodo_https___doi_org_10_5281_zenodo_16894800
institution Zenodo
language eng
publishDate 2025
publisher Zenodo
record_format zenodo
spellingShingle Preprint of "BEST-CSP benchmark study of polymorphs I and II of sulfamerazine and the perils of polytype polymorphs"
Červinka, Ctirad
Bouzek, Karel
Paušová, Šárka
VZ4
214021
214023
VSCHT
sulfamerazine
molecular crystals
polymorphism
quasi-harmonic approximation
ab initio calculations
We report the outcome of an interdisciplinary investigation by the BEST-CSP network of the kinetically favoured form I and the low temperature stable form II of the drug sulfamerazine (SMZ). A new structure determination of form II at 150 K is presented, allowing a better comparison with form I (SLFNMA04). Attempts to find the solvent-mediated transition temperature were complicated by observing that various slurrying experiments produce a new polymorph, sulfamerazine Form V, which is closely related to form I but with an alternative packing of the double layers, i.e. is a polytype polymorph. Forms I and V are only distinguishable by high-quality X-ray diffraction. Form V appears to be marginally more stable than form I above 50 °C. The experimental data, including heat capacities and thermal expansion are used to test a wide range of assumptions and energy models for calculating free energy differences between these, polymorphs, in particular the composite quasi-harmonic approximation, relying on DFT and DFTB quantum-chemical theories. This work illustrates the challenges in computational the thermodynamic transition temperature between form I and II. The complications caused by the discovery of form V are discussed.
title Preprint of "BEST-CSP benchmark study of polymorphs I and II of sulfamerazine and the perils of polytype polymorphs"
topic VZ4
214021
214023
VSCHT
sulfamerazine
molecular crystals
polymorphism
quasi-harmonic approximation
ab initio calculations
url https://doi.org/10.5281/zenodo.16894800