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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...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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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. |
format | Online Article Text |
id | pubmed-8640990 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
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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