Tautomerism in acyl-pyrazolones and in a novel photolysis product—importance and impact of the accurate localization of hydrogen atoms in crystal structures

Malaspina, Lorraine A.; White, Allan H.; Wege, Dieter; Tolmie, Michael B.; Skelton, Brian W.; Grabowsky, Simon (2017). Tautomerism in acyl-pyrazolones and in a novel photolysis product—importance and impact of the accurate localization of hydrogen atoms in crystal structures. Structural chemistry, 28(5), pp. 1343-1357. Springer 10.1007/s11224-017-1005-0

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Acyl-pyrazolones exist in four different tautomeric forms (two keto and two enol) in crystal structures. Routine crystal structure refinements using an independent atom model and routine isolated-molecule calculations fail in locating the mobile hydrogen atoms accurately in 22 investigated acyl-pyrazolone examples. However, a combination of both within the framework of quantum crystallography represented by the method of Hirshfeld atom refinement accurately locates the mobile hydrogen atom in a resonance-assisted hydrogen bond of title compound 3, a novel photolysis product. The impact of the hydrogen atom position on the resonance system of the non-hydrogen framework of the various tautomers is discussed, and the importance of intermolecular interactions for the positioning of the hydrogen atom is highlighted.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Grabowsky, Simon

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

1040-0400

Publisher:

Springer

Language:

English

Submitter:

Simon Grabowsky

Date Deposited:

06 Feb 2020 11:56

Last Modified:

06 Feb 2020 11:56

Publisher DOI:

10.1007/s11224-017-1005-0

BORIS DOI:

10.7892/boris.138430

URI:

https://boris.unibe.ch/id/eprint/138430

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