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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.

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More information

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

Identifiers

Local EPrints ID: 343456
URI: https://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: 19 Jul 2019 00:41

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