Origins of isotopomeric polymorphism

Jun Zhou, Young Sik Kye, Alexander Kolesnikov, Gerard Harbison

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The complex formed between 4-methylpyridine and pentachlorophenol (4MPPCP) crystallises in a triclinic space group. If the same complex is synthesized from deuterated pentachlorophenol, it crystallizes in an entirely different monoclinic polymorph. Using solid-state NMR of samples synthesized with a full range of deuteration levels, crystallized from solution or the melt, and in the presence or absence of seeds, we have confirmed that the isotopomers indeed have different thermodynamically stable crystal structures. The roots of this phenomenon of isotopomeric polymorphism apparently lie in the differences in hydrogen bonding between the polymorphs. The triclinic form has a relatively short hydrogen bond. High-field solid-state NMR shows both the 1H chemical shift and the 2H electric quadrupole coupling of the hydrogen involved in the bond to be strongly temperature-dependent, indicating a low-lying excited state of the hydrogen bond longitudinal vibration. Inelastic neutron scattering of isotopomers of 4MPPCP has allowed us to identify the three orthogonal vibrational modes of the hydrogen in the hydrogen bond, at 29.7, 145, and 205 meV (240, 1168, and 1651 cm-1). The longitudinal mode is the lowest in energy, and it indicates a slightly asymmetric low-barrier double-well potential. Intrinsic to such potentials is a very small difference in zero-point energies (ZPEs) between the protonated and deuterated forms. As a contrast, the monoclinic form has a comparatively normal hydrogen bond, in which the proton and deuteron ZPEs should be different by approximately 500 cm-1. A scenario can be envisaged where the triclinic protonated form is lower in energy than the monoclinic protonated form, but the triclinic deuterated form is higher in energy than the monoclinic deuterated form. This evidently accounts for the difference in relative stabilities of the two forms upon isotope substitution.

Original languageEnglish (US)
Pages (from-to)271-277
Number of pages7
JournalIsotopes in Environmental and Health Studies
Volume42
Issue number3
DOIs
StatePublished - Sep 1 2006

Fingerprint

Polymorphism
Hydrogen bonds
polymorphism
hydrogen
PCP
Hydrogen
energy
Nuclear magnetic resonance
Pentachlorophenol
nuclear magnetic resonance
Inelastic neutron scattering
Deuterium
Chemical shift
neutron scattering
Excited states
Isotopes
Seed
Protons
Substitution reactions
Crystal structure

Keywords

  • Crystal structures
  • Hydrogen bonds
  • Hydrogen-2
  • Isotope effects
  • Isotopomers
  • NMR
  • Organic crystals
  • Polymorphism

ASJC Scopus subject areas

  • Environmental Chemistry
  • Environmental Science(all)
  • Inorganic Chemistry

Cite this

Origins of isotopomeric polymorphism. / Zhou, Jun; Kye, Young Sik; Kolesnikov, Alexander; Harbison, Gerard.

In: Isotopes in Environmental and Health Studies, Vol. 42, No. 3, 01.09.2006, p. 271-277.

Research output: Contribution to journalArticle

Zhou, Jun ; Kye, Young Sik ; Kolesnikov, Alexander ; Harbison, Gerard. / Origins of isotopomeric polymorphism. In: Isotopes in Environmental and Health Studies. 2006 ; Vol. 42, No. 3. pp. 271-277.
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AB - The complex formed between 4-methylpyridine and pentachlorophenol (4MPPCP) crystallises in a triclinic space group. If the same complex is synthesized from deuterated pentachlorophenol, it crystallizes in an entirely different monoclinic polymorph. Using solid-state NMR of samples synthesized with a full range of deuteration levels, crystallized from solution or the melt, and in the presence or absence of seeds, we have confirmed that the isotopomers indeed have different thermodynamically stable crystal structures. The roots of this phenomenon of isotopomeric polymorphism apparently lie in the differences in hydrogen bonding between the polymorphs. The triclinic form has a relatively short hydrogen bond. High-field solid-state NMR shows both the 1H chemical shift and the 2H electric quadrupole coupling of the hydrogen involved in the bond to be strongly temperature-dependent, indicating a low-lying excited state of the hydrogen bond longitudinal vibration. Inelastic neutron scattering of isotopomers of 4MPPCP has allowed us to identify the three orthogonal vibrational modes of the hydrogen in the hydrogen bond, at 29.7, 145, and 205 meV (240, 1168, and 1651 cm-1). The longitudinal mode is the lowest in energy, and it indicates a slightly asymmetric low-barrier double-well potential. Intrinsic to such potentials is a very small difference in zero-point energies (ZPEs) between the protonated and deuterated forms. As a contrast, the monoclinic form has a comparatively normal hydrogen bond, in which the proton and deuteron ZPEs should be different by approximately 500 cm-1. A scenario can be envisaged where the triclinic protonated form is lower in energy than the monoclinic protonated form, but the triclinic deuterated form is higher in energy than the monoclinic deuterated form. This evidently accounts for the difference in relative stabilities of the two forms upon isotope substitution.

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KW - NMR

KW - Organic crystals

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