High-pressure polymorphism in pyridine
Single crystals of the high-pressure phases II and III of pyridine have been obtained by in situ crystallization at 1.09 and 1.69 GPa, revealing the crystal structure of phase III for the first time using X-ray diffraction. Phase II crystallizes in P212121 with Z′ = 1 and phase III in P41212 with Z′...
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International Union of Crystallography
2020-01-01
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doaj-0c06cf1111a74892bace30884675651c2020-11-25T02:34:06ZengInternational Union of CrystallographyIUCrJ2052-25252020-01-0171587010.1107/S2052252519015616lq5025High-pressure polymorphism in pyridineNico Giordano0Christine M. Beavers1Branton J. Campbell2Václav Eigner3Eugene Gregoryanz4Willliam G. Marshall5Miriam Peña-Álvarez6Simon J. Teat7Cara E. Vennari8Simon Parsons9Centre for Science at Extreme Conditions and EastChem School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, UKAdvanced Light Source, Lawrence Berkeley National Laboratory, Berkley, CA 94720, USADepartment of Physics and Astronomy, Brigham Young University, Provo, UT 84602, USACentre for Science at Extreme Conditions and EastChem School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, UKSchool of Physics and Astronomy and the Centre for Science at Extreme Conditions, University of Edinburgh, Edinburgh EH9 3FD, UKISIS Neutron and Muon Source, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell, Didcot OX11 0QX, UKSchool of Physics and Astronomy and the Centre for Science at Extreme Conditions, University of Edinburgh, Edinburgh EH9 3FD, UKAdvanced Light Source, Lawrence Berkeley National Laboratory, Berkley, CA 94720, USAAdvanced Light Source, Lawrence Berkeley National Laboratory, Berkley, CA 94720, USACentre for Science at Extreme Conditions and EastChem School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, UKSingle crystals of the high-pressure phases II and III of pyridine have been obtained by in situ crystallization at 1.09 and 1.69 GPa, revealing the crystal structure of phase III for the first time using X-ray diffraction. Phase II crystallizes in P212121 with Z′ = 1 and phase III in P41212 with Z′ = ½. Neutron powder diffraction experiments using pyridine-d5 establish approximate equations of state of both phases. The space group and unit-cell dimensions of phase III are similar to the structures of other simple compounds with C2v molecular symmetry, and the phase becomes stable at high pressure because it is topologically close-packed, resulting in a lower molar volume than the topologically body-centred cubic phase II. Phases II and III have been observed previously by Raman spectroscopy, but have been mis-identified or inconsistently named. Raman spectra collected on the same samples as used in the X-ray experiments establish the vibrational characteristics of both phases unambiguously. The pyridine molecules interact in both phases through CH...π and CH...N interactions. The nature of individual contacts is preserved through the phase transition between phases III and II, which occurs on decompression. A combination of rigid-body symmetry mode analysis and density functional theory calculations enables the soft vibrational lattice mode which governs the transformation to be identified.http://scripts.iucr.org/cgi-bin/paper?S2052252519015616polymorphismpressurein situ crystallizationphase transitions |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Nico Giordano Christine M. Beavers Branton J. Campbell Václav Eigner Eugene Gregoryanz Willliam G. Marshall Miriam Peña-Álvarez Simon J. Teat Cara E. Vennari Simon Parsons |
spellingShingle |
Nico Giordano Christine M. Beavers Branton J. Campbell Václav Eigner Eugene Gregoryanz Willliam G. Marshall Miriam Peña-Álvarez Simon J. Teat Cara E. Vennari Simon Parsons High-pressure polymorphism in pyridine IUCrJ polymorphism pressure in situ crystallization phase transitions |
author_facet |
Nico Giordano Christine M. Beavers Branton J. Campbell Václav Eigner Eugene Gregoryanz Willliam G. Marshall Miriam Peña-Álvarez Simon J. Teat Cara E. Vennari Simon Parsons |
author_sort |
Nico Giordano |
title |
High-pressure polymorphism in pyridine |
title_short |
High-pressure polymorphism in pyridine |
title_full |
High-pressure polymorphism in pyridine |
title_fullStr |
High-pressure polymorphism in pyridine |
title_full_unstemmed |
High-pressure polymorphism in pyridine |
title_sort |
high-pressure polymorphism in pyridine |
publisher |
International Union of Crystallography |
series |
IUCrJ |
issn |
2052-2525 |
publishDate |
2020-01-01 |
description |
Single crystals of the high-pressure phases II and III of pyridine have been obtained by in situ crystallization at 1.09 and 1.69 GPa, revealing the crystal structure of phase III for the first time using X-ray diffraction. Phase II crystallizes in P212121 with Z′ = 1 and phase III in P41212 with Z′ = ½. Neutron powder diffraction experiments using pyridine-d5 establish approximate equations of state of both phases. The space group and unit-cell dimensions of phase III are similar to the structures of other simple compounds with C2v molecular symmetry, and the phase becomes stable at high pressure because it is topologically close-packed, resulting in a lower molar volume than the topologically body-centred cubic phase II. Phases II and III have been observed previously by Raman spectroscopy, but have been mis-identified or inconsistently named. Raman spectra collected on the same samples as used in the X-ray experiments establish the vibrational characteristics of both phases unambiguously. The pyridine molecules interact in both phases through CH...π and CH...N interactions. The nature of individual contacts is preserved through the phase transition between phases III and II, which occurs on decompression. A combination of rigid-body symmetry mode analysis and density functional theory calculations enables the soft vibrational lattice mode which governs the transformation to be identified. |
topic |
polymorphism pressure in situ crystallization phase transitions |
url |
http://scripts.iucr.org/cgi-bin/paper?S2052252519015616 |
work_keys_str_mv |
AT nicogiordano highpressurepolymorphisminpyridine AT christinembeavers highpressurepolymorphisminpyridine AT brantonjcampbell highpressurepolymorphisminpyridine AT vaclaveigner highpressurepolymorphisminpyridine AT eugenegregoryanz highpressurepolymorphisminpyridine AT willliamgmarshall highpressurepolymorphisminpyridine AT miriampenaalvarez highpressurepolymorphisminpyridine AT simonjteat highpressurepolymorphisminpyridine AT caraevennari highpressurepolymorphisminpyridine AT simonparsons highpressurepolymorphisminpyridine |
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1724810077082222592 |