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Title: High-pressure polymorphism in pyridine

Journal Article · · IUCrJ
 [1];  [2];  [3];  [4];  [5]; ORCiD logo [6];  [5];  [7];  [8];  [5]
  1. Univ. of Edinburgh (United Kingdom); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Deutsches Elektonen-Synchrotron (DESY), Hamberg (Germany)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Santa Cruz, CA (United States); Rutherford Appleton Lab., Didcot (United Kingdom)
  3. Brigham Young Univ., Provo, UT (United States)
  4. Univ. of Edinburgh (United Kingdom); Inst. of Physics of the Academy of Sciences of the Czech Republic, Prague (Czech Republic)
  5. Univ. of Edinburgh (United Kingdom)
  6. Rutherford Appleton Lab., Didcot (United Kingdom)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  8. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS); Univ. of California, Santa Cruz, CA (United States)

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1577894
Alternate ID(s):
OSTI ID: 1599833
Journal Information:
IUCrJ, Vol. 7, Issue 1; ISSN 2052-2525
Publisher:
International Union of CrystallographyCopyright Statement
Country of Publication:
United States
Language:
English

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