Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO2Clathrate

Arnaud Grosjean; Peter R. Spackman; Alison J. Edwards; Kasper Tolborg; Emilie S. Vosegaard; George A. Koutsantonis; Bo B. Iversen; Mark A. Spackman

doi:10.1021/acs.cgd.1c00271

Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO₂Clathrate

Arnaud Grosjean, Peter R. Spackman, Alison J. Edwards, Kasper Tolborg, Emilie S. Vosegaard, George A. Koutsantonis^*, Bo B. Iversen, Mark A. Spackman^*

^*Corresponding author for this work

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Abstract

High-resolution 100 K X-ray and neutron single-crystal diffraction data of the non-stoichiometric hydroquinone-CO2 (HQ-CO2) clathrate are combined, with the aim of providing further insight into host-guest binding in hydroquinone clathrates, measuring the electrostatic nature of the cavity formed by the HQ host and, for the first time, estimating the quadrupole moment of the CO2 guest molecule via diffraction techniques. The experimental electron density reveals the cavity in the β-HQ structure to be moderately electronegative and largely featureless, but this does not mean that guest molecules are merely trapped. Calculated binding energies for a series of HQ clathrates reveal strong interactions with the host system and, in the case of CO2, a thermodynamic stability comparable to, or exceeding, that of many molecular cocrystals. The remarkable flexibility of the β-HQ host structure is explored through an analysis of its available clathrate structures at 100 K as well as calculated elastic tensors for crystals of β-HQ and the HQ-CO2 clathrate. Establishing the CO2 quadrupole moment from this analysis of the experimental diffraction data proves challenging, but the sign and estimated range of its magnitude are in agreement with spectroscopic measurements in the gas phase.

Original language	English
Journal	Crystal Growth and Design
Volume	21
Issue	6
Pages (from-to)	3477-3486
Number of pages	10
ISSN	1528-7483
DOIs	https://doi.org/10.1021/acs.cgd.1c00271
Publication status	Published - Jun 2021

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Grosjean, A., Spackman, P. R., Edwards, A. J., Tolborg, K., Vosegaard, E. S., Koutsantonis, G. A., Iversen, B. B., & Spackman, M. A. (2021). Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO₂Clathrate. Crystal Growth and Design, 21(6), 3477-3486. https://doi.org/10.1021/acs.cgd.1c00271

@article{5f93308d49414861abecd7ffc550cd2e,

title = "Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO2Clathrate",

abstract = "High-resolution 100 K X-ray and neutron single-crystal diffraction data of the non-stoichiometric hydroquinone-CO2 (HQ-CO2) clathrate are combined, with the aim of providing further insight into host-guest binding in hydroquinone clathrates, measuring the electrostatic nature of the cavity formed by the HQ host and, for the first time, estimating the quadrupole moment of the CO2 guest molecule via diffraction techniques. The experimental electron density reveals the cavity in the β-HQ structure to be moderately electronegative and largely featureless, but this does not mean that guest molecules are merely trapped. Calculated binding energies for a series of HQ clathrates reveal strong interactions with the host system and, in the case of CO2, a thermodynamic stability comparable to, or exceeding, that of many molecular cocrystals. The remarkable flexibility of the β-HQ host structure is explored through an analysis of its available clathrate structures at 100 K as well as calculated elastic tensors for crystals of β-HQ and the HQ-CO2 clathrate. Establishing the CO2 quadrupole moment from this analysis of the experimental diffraction data proves challenging, but the sign and estimated range of its magnitude are in agreement with spectroscopic measurements in the gas phase. ",

author = "Arnaud Grosjean and Spackman, {Peter R.} and Edwards, {Alison J.} and Kasper Tolborg and Vosegaard, {Emilie S.} and Koutsantonis, {George A.} and Iversen, {Bo B.} and Spackman, {Mark A.}",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society",

year = "2021",

month = jun,

doi = "10.1021/acs.cgd.1c00271",

language = "English",

volume = "21",

pages = "3477--3486",

journal = "Crystal Growth and Design",

issn = "1528-7483",

publisher = "AMER CHEMICAL SOC",

number = "6",

}

Grosjean, A, Spackman, PR, Edwards, AJ, Tolborg, K, Vosegaard, ES, Koutsantonis, GA, Iversen, BB & Spackman, MA 2021, 'Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO₂Clathrate', Crystal Growth and Design, vol. 21, no. 6, pp. 3477-3486. https://doi.org/10.1021/acs.cgd.1c00271

Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO₂Clathrate. / Grosjean, Arnaud; Spackman, Peter R.; Edwards, Alison J. et al.
In: Crystal Growth and Design, Vol. 21, No. 6, 06.2021, p. 3477-3486.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Insights into Host-Guest Binding in Hydroquinone Clathrates

T2 - Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO2Clathrate

AU - Grosjean, Arnaud

AU - Spackman, Peter R.

AU - Edwards, Alison J.

AU - Tolborg, Kasper

AU - Vosegaard, Emilie S.

AU - Koutsantonis, George A.

AU - Iversen, Bo B.

AU - Spackman, Mark A.

PY - 2021/6

Y1 - 2021/6

N2 - High-resolution 100 K X-ray and neutron single-crystal diffraction data of the non-stoichiometric hydroquinone-CO2 (HQ-CO2) clathrate are combined, with the aim of providing further insight into host-guest binding in hydroquinone clathrates, measuring the electrostatic nature of the cavity formed by the HQ host and, for the first time, estimating the quadrupole moment of the CO2 guest molecule via diffraction techniques. The experimental electron density reveals the cavity in the β-HQ structure to be moderately electronegative and largely featureless, but this does not mean that guest molecules are merely trapped. Calculated binding energies for a series of HQ clathrates reveal strong interactions with the host system and, in the case of CO2, a thermodynamic stability comparable to, or exceeding, that of many molecular cocrystals. The remarkable flexibility of the β-HQ host structure is explored through an analysis of its available clathrate structures at 100 K as well as calculated elastic tensors for crystals of β-HQ and the HQ-CO2 clathrate. Establishing the CO2 quadrupole moment from this analysis of the experimental diffraction data proves challenging, but the sign and estimated range of its magnitude are in agreement with spectroscopic measurements in the gas phase.

AB - High-resolution 100 K X-ray and neutron single-crystal diffraction data of the non-stoichiometric hydroquinone-CO2 (HQ-CO2) clathrate are combined, with the aim of providing further insight into host-guest binding in hydroquinone clathrates, measuring the electrostatic nature of the cavity formed by the HQ host and, for the first time, estimating the quadrupole moment of the CO2 guest molecule via diffraction techniques. The experimental electron density reveals the cavity in the β-HQ structure to be moderately electronegative and largely featureless, but this does not mean that guest molecules are merely trapped. Calculated binding energies for a series of HQ clathrates reveal strong interactions with the host system and, in the case of CO2, a thermodynamic stability comparable to, or exceeding, that of many molecular cocrystals. The remarkable flexibility of the β-HQ host structure is explored through an analysis of its available clathrate structures at 100 K as well as calculated elastic tensors for crystals of β-HQ and the HQ-CO2 clathrate. Establishing the CO2 quadrupole moment from this analysis of the experimental diffraction data proves challenging, but the sign and estimated range of its magnitude are in agreement with spectroscopic measurements in the gas phase.

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U2 - 10.1021/acs.cgd.1c00271

DO - 10.1021/acs.cgd.1c00271

M3 - Journal article

AN - SCOPUS:85106523619

SN - 1528-7483

VL - 21

SP - 3477

EP - 3486

JO - Crystal Growth and Design

JF - Crystal Growth and Design

IS - 6

ER -

Insights into Host-Guest Binding in Hydroquinone Clathrates: Single-Crystal X-ray and Neutron Diffraction, and Complementary Computational Studies on the Hydroquinone-CO₂Clathrate

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