Structures of the monofluoro- and monochlorophenols at low temperature and high pressure

I D H Oswald, D R Allan, W D S Motherwell, S Parsons

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

2-Fluorophenol, 3-fluorophenol and 3-chlorophenol were recrystallized from frozen solids at 260, 263 and 283 K. All compounds were also crystallized by the application of high pressure (0.36, 0.12 and 0.10 GPa). While 3-fluorophenol and 3-chlorophenol yielded the same phases under both conditions, different polymorphs were obtained for 2-fluorophenol. 4-Chlorophenol was crystallized both from the melt and from benzene to yield two different ambient-pressure polymorphs; crystallization from the melt at 0.02 GPa yielded the same phase as from benzene at ambient pressure. 3-Fluorophenol is unusual in forming a hydrogen-bonded chain along a 2(1) screw axis. Such behaviour is usually only observed for small alcohols, but here it appears to be stabilized by intermolecular C - H ... F hydrogen-bond formation. 3-Chlorophenol is a more typical large alcohol and emulates a fourfold screw axis with two independent molecules positioned about a 2(1) axis, although there are significant distortions from this ideal geometry. The two phases of 4-chlorophenol consist of chains or rings connected by C - Cl ... H interactions. The low-temperature and high-pressure polymorphs of 2-fluorophenol consist of chains of molecules connected through OH ... OH hydrogen bonds; while inter-chain C - H ... F interactions are significant at high pressure, there are none in the low-temperature form.

LanguageEnglish
Pages69-79
Number of pages11
JournalActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials
Volume61
Issue numberPart 1
DOIs
Publication statusPublished - Feb 2005

Fingerprint

Pressure
Polymorphism
Temperature
screws
Hydrogen
Benzene
alcohols
benzene
hydrogen bonds
Hydrogen bonds
Alcohols
Molecules
molecules
Crystallization
interactions
crystallization
rings
hydrogen
geometry
Geometry

Keywords

  • X-ray diffraction
  • crystal structures
  • database
  • phenols
  • polymorphism
  • hydrogen bonding
  • high pressure
  • low temperature

Cite this

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title = "Structures of the monofluoro- and monochlorophenols at low temperature and high pressure",
abstract = "2-Fluorophenol, 3-fluorophenol and 3-chlorophenol were recrystallized from frozen solids at 260, 263 and 283 K. All compounds were also crystallized by the application of high pressure (0.36, 0.12 and 0.10 GPa). While 3-fluorophenol and 3-chlorophenol yielded the same phases under both conditions, different polymorphs were obtained for 2-fluorophenol. 4-Chlorophenol was crystallized both from the melt and from benzene to yield two different ambient-pressure polymorphs; crystallization from the melt at 0.02 GPa yielded the same phase as from benzene at ambient pressure. 3-Fluorophenol is unusual in forming a hydrogen-bonded chain along a 2(1) screw axis. Such behaviour is usually only observed for small alcohols, but here it appears to be stabilized by intermolecular C - H ... F hydrogen-bond formation. 3-Chlorophenol is a more typical large alcohol and emulates a fourfold screw axis with two independent molecules positioned about a 2(1) axis, although there are significant distortions from this ideal geometry. The two phases of 4-chlorophenol consist of chains or rings connected by C - Cl ... H interactions. The low-temperature and high-pressure polymorphs of 2-fluorophenol consist of chains of molecules connected through OH ... OH hydrogen bonds; while inter-chain C - H ... F interactions are significant at high pressure, there are none in the low-temperature form.",
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author = "Oswald, {I D H} and Allan, {D R} and Motherwell, {W D S} and S Parsons",
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Structures of the monofluoro- and monochlorophenols at low temperature and high pressure. / Oswald, I D H ; Allan, D R ; Motherwell, W D S ; Parsons, S .

In: Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, Vol. 61, No. Part 1, 02.2005, p. 69-79.

Research output: Contribution to journalArticle

TY - JOUR

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AU - Oswald, I D H

AU - Allan, D R

AU - Motherwell, W D S

AU - Parsons, S

PY - 2005/2

Y1 - 2005/2

N2 - 2-Fluorophenol, 3-fluorophenol and 3-chlorophenol were recrystallized from frozen solids at 260, 263 and 283 K. All compounds were also crystallized by the application of high pressure (0.36, 0.12 and 0.10 GPa). While 3-fluorophenol and 3-chlorophenol yielded the same phases under both conditions, different polymorphs were obtained for 2-fluorophenol. 4-Chlorophenol was crystallized both from the melt and from benzene to yield two different ambient-pressure polymorphs; crystallization from the melt at 0.02 GPa yielded the same phase as from benzene at ambient pressure. 3-Fluorophenol is unusual in forming a hydrogen-bonded chain along a 2(1) screw axis. Such behaviour is usually only observed for small alcohols, but here it appears to be stabilized by intermolecular C - H ... F hydrogen-bond formation. 3-Chlorophenol is a more typical large alcohol and emulates a fourfold screw axis with two independent molecules positioned about a 2(1) axis, although there are significant distortions from this ideal geometry. The two phases of 4-chlorophenol consist of chains or rings connected by C - Cl ... H interactions. The low-temperature and high-pressure polymorphs of 2-fluorophenol consist of chains of molecules connected through OH ... OH hydrogen bonds; while inter-chain C - H ... F interactions are significant at high pressure, there are none in the low-temperature form.

AB - 2-Fluorophenol, 3-fluorophenol and 3-chlorophenol were recrystallized from frozen solids at 260, 263 and 283 K. All compounds were also crystallized by the application of high pressure (0.36, 0.12 and 0.10 GPa). While 3-fluorophenol and 3-chlorophenol yielded the same phases under both conditions, different polymorphs were obtained for 2-fluorophenol. 4-Chlorophenol was crystallized both from the melt and from benzene to yield two different ambient-pressure polymorphs; crystallization from the melt at 0.02 GPa yielded the same phase as from benzene at ambient pressure. 3-Fluorophenol is unusual in forming a hydrogen-bonded chain along a 2(1) screw axis. Such behaviour is usually only observed for small alcohols, but here it appears to be stabilized by intermolecular C - H ... F hydrogen-bond formation. 3-Chlorophenol is a more typical large alcohol and emulates a fourfold screw axis with two independent molecules positioned about a 2(1) axis, although there are significant distortions from this ideal geometry. The two phases of 4-chlorophenol consist of chains or rings connected by C - Cl ... H interactions. The low-temperature and high-pressure polymorphs of 2-fluorophenol consist of chains of molecules connected through OH ... OH hydrogen bonds; while inter-chain C - H ... F interactions are significant at high pressure, there are none in the low-temperature form.

KW - X-ray diffraction

KW - crystal structures

KW - database

KW - phenols

KW - polymorphism

KW - hydrogen bonding

KW - high pressure

KW - low temperature

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JO - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

T2 - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

JF - Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

SN - 2052-5192

IS - Part 1

ER -