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

A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates
A multinuclear solid state NMR, density functional theory and X-Ray diffraction study of hydrogen bonding in Group I hydrogen dibenzoates
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 H-1 and C-13 MAS NMR methods provide primary descriptions of the H bonding via accurate measurements of the H-1 and C-13 isotropic chemical shifts, and the individual C-13 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, O-17 MAS and DOR NMR form a powerful combination to characterise the O environments, with the DOR technique providing highly resolved O-17 NMR data which helps verify unequivocally the number of inequivalent O positions for the conventional O-17 MAS NMR to process. Further multinuclear MAS and static NMR studies involving the quadrupolar Li-7, K-39, Rb-87 and Cs-133 nuclei, and the associated DFT calculations, provide trends and a corroboration of the H bond geometry which assist in the understanding of these arrangements. Even though the crystallographic H positions in each H bonding arrangement reported from the single crystal X-ray studies are prone to uncertainty, the good corroboration between the measured and DFT calculated chemical shift and quadrupole tensor parameters for the Group I alkali species suggest that these reported H positions are reliable.
1466-8033
8823-8839
Rees, Gregory J.
2a9e69dd-adf4-4c26-8e53-86d3c7f64397
Day, Stephen P.
370c1e67-64c9-41d2-b505-6da22b641a2c
Lari, Alberth
70ed7535-a94e-4553-ab42-fd960642d916
Howes, Andrew P.
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Iuga, Dinu
280c6d9a-aeca-4bf7-8510-b4588556d530
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Threlfall, Terry L.
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Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Smith, Mark E.
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Quigley, David
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Wallis, John D.
bc777046-08c0-40bf-9cfd-3a69481bb06a
Hanna, John V.
20ab8960-4ac0-41c7-bc4a-a40195717a51
Rees, Gregory J.
2a9e69dd-adf4-4c26-8e53-86d3c7f64397
Day, Stephen P.
370c1e67-64c9-41d2-b505-6da22b641a2c
Lari, Alberth
70ed7535-a94e-4553-ab42-fd960642d916
Howes, Andrew P.
0a03c3cf-013b-4908-a09c-a4ceb9049aec
Iuga, Dinu
280c6d9a-aeca-4bf7-8510-b4588556d530
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Threlfall, Terry L.
6c670746-9730-49fc-9381-e45ae4807450
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Smith, Mark E.
4451f517-53c8-455a-b86d-7448d5c3125f
Quigley, David
1b041352-ccc3-4a42-b7e7-945749a8c2cb
Wallis, John D.
bc777046-08c0-40bf-9cfd-3a69481bb06a
Hanna, John V.
20ab8960-4ac0-41c7-bc4a-a40195717a51

Rees, Gregory J., Day, Stephen P., Lari, Alberth, Howes, Andrew P., Iuga, Dinu, Pitak, Mateusz B., Coles, Simon J., Threlfall, Terry L., Light, Mark E., Smith, Mark E., Quigley, David, Wallis, John D. and Hanna, John 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), 8823-8839. (doi:10.1039/c3ce41258j).

Record type: Article

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 H-1 and C-13 MAS NMR methods provide primary descriptions of the H bonding via accurate measurements of the H-1 and C-13 isotropic chemical shifts, and the individual C-13 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, O-17 MAS and DOR NMR form a powerful combination to characterise the O environments, with the DOR technique providing highly resolved O-17 NMR data which helps verify unequivocally the number of inequivalent O positions for the conventional O-17 MAS NMR to process. Further multinuclear MAS and static NMR studies involving the quadrupolar Li-7, K-39, Rb-87 and Cs-133 nuclei, and the associated DFT calculations, provide trends and a corroboration of the H bond geometry which assist in the understanding of these arrangements. Even though the crystallographic H positions in each H bonding arrangement reported from the single crystal X-ray studies are prone to uncertainty, the good corroboration between the measured and DFT calculated chemical shift and quadrupole tensor parameters for the Group I alkali species suggest that these reported H positions are reliable.

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More information

Published date: 2013
Additional Information: Funded by EPSRC: Bond Formation Studies By Charge Density Measurements and Solid State 17O NMR Spectrometry (EP/E018203/1)
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 362484
URI: http://eprints.soton.ac.uk/id/eprint/362484
ISSN: 1466-8033
PURE UUID: 5d1d1a3e-6c90-4adb-9933-d2788adeefd5
ORCID for Mateusz B. Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843

Catalogue record

Date deposited: 25 Feb 2014 13:57
Last modified: 18 Feb 2021 16:53

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Contributors

Author: Gregory J. Rees
Author: Stephen P. Day
Author: Alberth Lari
Author: Andrew P. Howes
Author: Dinu Iuga
Author: Mateusz B. Pitak ORCID iD
Author: Simon J. Coles ORCID iD
Author: Terry L. Threlfall
Author: Mark E. Light ORCID iD
Author: Mark E. Smith
Author: David Quigley
Author: John D. Wallis
Author: John V. Hanna

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