A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates

Rees, G.J., Day, S.P., Lari, A., Howes, A.P., Iuga, D., Pitak, M.B., Coles, S.J., Threlfall, T.L., Light, M.E., Smith, M.E., Quigley, D., Wallis, J.D. ORCID: 0000-0001-7259-8783 and Hanna, J.V., 2013. A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates. CrystEngComm, 15 (43), pp. 8823-8839. ISSN 1466-8033

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Abstract

An NMR crystallographic approach incorporating multinuclear solid state NMR (SSNMR), X-ray structure determinations and density functional theory (DFT) are used to characterise the H bonding arrangements in benzoic acid (BZA) and the corresponding Group I alkali metal hydrogen dibenzoates (HD) systems. Since the XRD data often cannot precisely confirm the proton position within the hydrogen bond, the relationship between the experimental SSNMR parameters and the ability of gauge included plane augmented wave (GIPAW) DFT to predict them becomes a powerful constraint that can assist with further structure refinement. Both the 1H and 13C MAS NMR methods provide primary descriptions of the H bonding via accurate measurements of the 1H and 13C isotropic chemical shifts, and the individual 13C chemical shift tensor elements; these are unequivocally corroborated by DFT calculations, which together accurately describe the trend of the H bonding strength as the size of the monovalent cation changes. In addition, 17O MAS and DOR NMR form a powerful combination to characterise the O environments, with the DOR technique providing highly resolved 17O NMR data which helps verify unequivocally the number of inequivalent O positions for the conventional 17O MAS NMR to process.

Item Type: Journal article
Publication Title: CrystEngComm
Creators: Rees, G.J., Day, S.P., Lari, A., Howes, A.P., Iuga, D., Pitak, M.B., Coles, S.J., Threlfall, T.L., Light, M.E., Smith, M.E., Quigley, D., Wallis, J.D. and Hanna, J.V.
Publisher: Royal Society of Chemistry
Place of Publication: Cambridge
Date: 2013
Volume: 15
Number: 43
ISSN: 1466-8033
Identifiers:
NumberType
10.1039/C3CE41258JDOI
Rights: © Royal Society of Chemistry 2013
Divisions: Schools > School of Science and Technology
Depositing User: EPrints Services
Date Added: 09 Oct 2015 10:54
Last Modified: 09 Jun 2017 13:44
URI: http://irep.ntu.ac.uk/id/eprint/19896

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