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Expanding the Solid Form Landscape of Bipyridines

[Image: see text] Two bipyridine isomers (2,2′- and 4,4′-), used as coformers and ligands in coordination chemistry, were subjected to solid form screening and crystal structure prediction. One anhydrate and a formic acid disolvate were crystallized for 2,2′-bipyridine, whereas multiple solid-state...

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Autores principales: Braun, Doris E., Hald, Patricia, Kahlenberg, Volker, Griesser, Ulrich J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8640990/
https://www.ncbi.nlm.nih.gov/pubmed/34867088
http://dx.doi.org/10.1021/acs.cgd.1c01045
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author Braun, Doris E.
Hald, Patricia
Kahlenberg, Volker
Griesser, Ulrich J.
author_facet Braun, Doris E.
Hald, Patricia
Kahlenberg, Volker
Griesser, Ulrich J.
author_sort Braun, Doris E.
collection PubMed
description [Image: see text] Two bipyridine isomers (2,2′- and 4,4′-), used as coformers and ligands in coordination chemistry, were subjected to solid form screening and crystal structure prediction. One anhydrate and a formic acid disolvate were crystallized for 2,2′-bipyridine, whereas multiple solid-state forms, anhydrate, dihydrate, and eight solvates with carboxylic acids, including a polymorphic acetic acid disolvate, were found for the 4,4′-isomer. Seven of the solvates are reported for the first time, and structural information is provided for six of the new solvates. All twelve solid-state forms were investigated comprehensively using experimental [thermal analysis, isothermal calorimetry, X-ray diffraction, gravimetric moisture (de)sorption, and IR spectroscopy] and computational approaches. Lattice and interaction energy calculations confirmed the thermodynamic driving force for disolvate formation, mediated by the absence of H-bond donor groups of the host molecules. The exposed location of the N atoms in 4,4′-bipyridine facilitates the accommodation of bigger carboxylic acids and leads to higher conformational flexibility compared to 2,2′-bipyridine. For the 4,4′-bipyridine anhydrate ↔ hydrate interconversion hardly any hysteresis and a fast transformation kinetics are observed, with the critical relative humidity being at 35% at room temperature. The computed anhydrate crystal energy landscapes have the 2,2′-bipyridine as the lowest energy structure and the 4,4′-bipyridine among the low-energy structures and suggest a different crystallization behavior of the two compounds.
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spelling pubmed-86409902021-12-03 Expanding the Solid Form Landscape of Bipyridines Braun, Doris E. Hald, Patricia Kahlenberg, Volker Griesser, Ulrich J. Cryst Growth Des [Image: see text] Two bipyridine isomers (2,2′- and 4,4′-), used as coformers and ligands in coordination chemistry, were subjected to solid form screening and crystal structure prediction. One anhydrate and a formic acid disolvate were crystallized for 2,2′-bipyridine, whereas multiple solid-state forms, anhydrate, dihydrate, and eight solvates with carboxylic acids, including a polymorphic acetic acid disolvate, were found for the 4,4′-isomer. Seven of the solvates are reported for the first time, and structural information is provided for six of the new solvates. All twelve solid-state forms were investigated comprehensively using experimental [thermal analysis, isothermal calorimetry, X-ray diffraction, gravimetric moisture (de)sorption, and IR spectroscopy] and computational approaches. Lattice and interaction energy calculations confirmed the thermodynamic driving force for disolvate formation, mediated by the absence of H-bond donor groups of the host molecules. The exposed location of the N atoms in 4,4′-bipyridine facilitates the accommodation of bigger carboxylic acids and leads to higher conformational flexibility compared to 2,2′-bipyridine. For the 4,4′-bipyridine anhydrate ↔ hydrate interconversion hardly any hysteresis and a fast transformation kinetics are observed, with the critical relative humidity being at 35% at room temperature. The computed anhydrate crystal energy landscapes have the 2,2′-bipyridine as the lowest energy structure and the 4,4′-bipyridine among the low-energy structures and suggest a different crystallization behavior of the two compounds. American Chemical Society 2021-11-10 2021-12-01 /pmc/articles/PMC8640990/ /pubmed/34867088 http://dx.doi.org/10.1021/acs.cgd.1c01045 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Braun, Doris E.
Hald, Patricia
Kahlenberg, Volker
Griesser, Ulrich J.
Expanding the Solid Form Landscape of Bipyridines
title Expanding the Solid Form Landscape of Bipyridines
title_full Expanding the Solid Form Landscape of Bipyridines
title_fullStr Expanding the Solid Form Landscape of Bipyridines
title_full_unstemmed Expanding the Solid Form Landscape of Bipyridines
title_short Expanding the Solid Form Landscape of Bipyridines
title_sort expanding the solid form landscape of bipyridines
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8640990/
https://www.ncbi.nlm.nih.gov/pubmed/34867088
http://dx.doi.org/10.1021/acs.cgd.1c01045
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