Crystal packing in the 2-R,4-oxo-[1,3-a/b]-naphthodioxanes – Hirshfeld surface analysis and melting point correlation

Grabowsky, Simon; Dean, Pamela M.; Skelton, Brian W.; Sobolev, Alexandre N.; Spackman, Mark A.; White, Allan H. (2012). Crystal packing in the 2-R,4-oxo-[1,3-a/b]-naphthodioxanes – Hirshfeld surface analysis and melting point correlation. CrystEngComm, 14(3), pp. 1083-1093. Royal Society of Chemistry 10.1039/C2CE06393J

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The crystal structures of an array of 2-R,4-oxo-[1,3-b]-naphthodioxanes (R = H, Me, Et, i-Pr, n-Bu, CCl3, i-propylideneglyceral) have been determined at 100 K, together with a more limited series of the isomeric 2-R,4-oxo-[1,3-a]-naphthodioxanes (R = Et, i-Pr, n-Bu, i-propylideneglyceral), permitting a study of the effects of substituent and ring fusion variation on the crystal packing of neutral molecules that are otherwise essentially planar. We have conducted an analysis of Hirshfeld surfaces (a definition of an outer contact surface of a molecule within a crystal) for all eleven compounds and follow the changes of different properties on these surfaces upon systematic variation of the substituent R. Not only qualitative information by means of fingerprint plots, but also quantitative information by means of melting point correlations are presented. The results show the extent to which C–H⋯O hydrogen bonds and C–H⋯π/π⋯π interactions contribute positively to the lattice energies on the one hand, and H⋯H contacts negatively on the other. The percentage of H⋯H contacts as closest contacts on the Hirshfeld surfaces is a universally applicable measure of the crystal lattice energy and can be used as a reference for the importance of other types of contacts.

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:

1466-8033

Publisher:

Royal Society of Chemistry

Language:

English

Submitter:

Simon Grabowsky

Date Deposited:

06 Feb 2020 09:49

Last Modified:

06 Feb 2020 09:49

Publisher DOI:

10.1039/C2CE06393J

BORIS DOI:

10.7892/boris.138484

URI:

https://boris.unibe.ch/id/eprint/138484

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