The University of Southampton
University of Southampton Institutional Repository

Realizing predicted crystal structures at extreme conditions: the low-temperature and high-pressure crystal structures of 2-chlorophenol and 4-fluorophenol

Realizing predicted crystal structures at extreme conditions: the low-temperature and high-pressure crystal structures of 2-chlorophenol and 4-fluorophenol
Realizing predicted crystal structures at extreme conditions: the low-temperature and high-pressure crystal structures of 2-chlorophenol and 4-fluorophenol
A crystal of 2-chlorophenol was grown from the liquid at ambient pressure by laser-assisted zone refinement; 4-fluorophenol was crystallized from ethanol. Different polymorphs were obtained at high pressure by compression of the liquids in a Merrill-Bassett diamond-anvil cell (crystallization pressures 0.12 and 0.28 GPa, respectively). The structures of all phases are characterized by OH---OH hydrogen-bond formation. In the ambient-pressure polymorph of 2-chlorophenol, a hydrogen-bonded chain is formed about a 32 screw-axis; the ambient-pressure phase of 4-fluorophenol contains hexameric rings located on 3 sites. In crystallizing in high-symmetry space groups, these two compounds conform to typical behavior for bulky monoalcohols. By contrast, at high-pressure both compounds form zigzag chains disposed about 21 screw-axes, behavior more characteristic of small monoalcohols. The halophenol moiety thus behaves as a bulky group at ambient pressure but a small group at high pressure. We show that Crystal Structure Prediction methodologies reproduce all four phases, even though the potentials used were developed using ambient-pressure data. This is especially encouraging as the ambient-pressure phase of 2-chlorophenol contains three molecules in the asymmetric unit, while the high-pressure phase of 4-fluorophenol is disordered.

1528-7483
1055-1071
Oswald, Iain D.H.
dd629683-d401-412d-bfe2-741b6fd757b0
Allan, David R.
311ec351-bbfd-4e05-bfd4-c571b7cb5f21
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Motherwell, W.D. Samuel
1eaf126c-8f3a-45b7-8a98-4a0493ee838e
Parsons, Simon
979d203f-915a-42f6-a6d7-3a5edaf834c6
Oswald, Iain D.H.
dd629683-d401-412d-bfe2-741b6fd757b0
Allan, David R.
311ec351-bbfd-4e05-bfd4-c571b7cb5f21
Day, Graeme M.
e3be79ba-ad12-4461-b735-74d5c4355636
Motherwell, W.D. Samuel
1eaf126c-8f3a-45b7-8a98-4a0493ee838e
Parsons, Simon
979d203f-915a-42f6-a6d7-3a5edaf834c6

Oswald, Iain D.H., Allan, David R., Day, Graeme M., Motherwell, W.D. Samuel and Parsons, Simon (2005) Realizing predicted crystal structures at extreme conditions: the low-temperature and high-pressure crystal structures of 2-chlorophenol and 4-fluorophenol. Crystal Growth & Design, 5 (3), 1055-1071. (doi:10.1021/cg049647b).

Record type: Article

Abstract

A crystal of 2-chlorophenol was grown from the liquid at ambient pressure by laser-assisted zone refinement; 4-fluorophenol was crystallized from ethanol. Different polymorphs were obtained at high pressure by compression of the liquids in a Merrill-Bassett diamond-anvil cell (crystallization pressures 0.12 and 0.28 GPa, respectively). The structures of all phases are characterized by OH---OH hydrogen-bond formation. In the ambient-pressure polymorph of 2-chlorophenol, a hydrogen-bonded chain is formed about a 32 screw-axis; the ambient-pressure phase of 4-fluorophenol contains hexameric rings located on 3 sites. In crystallizing in high-symmetry space groups, these two compounds conform to typical behavior for bulky monoalcohols. By contrast, at high-pressure both compounds form zigzag chains disposed about 21 screw-axes, behavior more characteristic of small monoalcohols. The halophenol moiety thus behaves as a bulky group at ambient pressure but a small group at high pressure. We show that Crystal Structure Prediction methodologies reproduce all four phases, even though the potentials used were developed using ambient-pressure data. This is especially encouraging as the ambient-pressure phase of 2-chlorophenol contains three molecules in the asymmetric unit, while the high-pressure phase of 4-fluorophenol is disordered.

This record has no associated files available for download.

More information

Published date: 2005
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Computational Systems Chemistry

Identifiers

Local EPrints ID: 343456
URI: http://eprints.soton.ac.uk/id/eprint/343456
ISSN: 1528-7483
PURE UUID: 3a3f023c-dd1c-4f62-ab98-bbfeadc7a6e7
ORCID for Graeme M. Day: ORCID iD orcid.org/0000-0001-8396-2771

Catalogue record

Date deposited: 05 Feb 2013 16:20
Last modified: 15 Mar 2024 03:44

Export record

Altmetrics

Contributors

Author: Iain D.H. Oswald
Author: David R. Allan
Author: Graeme M. Day ORCID iD
Author: W.D. Samuel Motherwell
Author: Simon Parsons

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×