Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles"

Qiang Zhu, Alexander G. Shtukenberg, Damien J. Carter, Tang Qing Yu, Jingxiang Yang, Ming Chen, Paolo Raiteri, Artem R. Oganov, Boaz Pokroy, Iryna Polishchuk, Peter J. Bygrave, Graeme M. Day, Andrew L. Rohl, Mark Tuckerman, Bart Kahr

Research output: Contribution to journalArticle

Abstract

Structures of the α and β phases of resorcinol, a major commodity chemical in the pharmaceutical, agrichemical, and polymer industries, were the first polymorphic pair of molecular crystals solved by X-ray analysis. It was recently stated that "no additional phases can be found under atmospheric conditions" (Druzbicki, K. et al. J. Phys. Chem. B 2015, 119, 1681). Herein is described the growth and structure of a new ambient pressure phase, ϵ, through a combination of optical and X-ray crystallography and by computational crystal structure prediction algorithms. α-Resorcinol has long been a model for mechanistic crystal growth studies from both solution and vapor because prisms extended along the polar axis grow much faster in one direction than in the opposite direction. Research has focused on identifying the absolute sense of the fast direction - the so-called "resorcinol riddle" - with the aim of identifying how solvent controls crystal growth. Here, the growth velocity dissymmetry in the melt is analyzed for the β phase. The ϵ phase only grows from the melt, concomitant with the β phase, as polycrystalline, radially growing spherulites. If the radii are polar, then the sense of the polar axis is an essential feature of the form. Here, this determination is made for spherulites of β resorcinol (ϵ, point symmetry 222, does not have a polar axis) with additives that stereoselectively modify growth velocities. Both β and ϵ have the additional feature that individual radial lamellae may adopt helicoidal morphologies. We correlate the appearance of twisting in β and ϵ with the symmetry of twist-inducing additives.

Original languageEnglish (US)
Pages (from-to)4881-4889
Number of pages9
JournalJournal of the American Chemical Society
Volume138
Issue number14
DOIs
StatePublished - Apr 27 2016

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Crystallization
Crystal growth
Molecular crystals
Growth
X ray crystallography
X ray analysis
Prisms
Agrochemicals
Drug products
X Ray Crystallography
Crystal structure
Vapors
Industry
Polymers
X-Rays
Pressure
resorcinol
Research
Pharmaceutical Preparations
Direction compound

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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Resorcinol Crystallization from the Melt : A New Ambient Phase and New "Riddles". / Zhu, Qiang; Shtukenberg, Alexander G.; Carter, Damien J.; Yu, Tang Qing; Yang, Jingxiang; Chen, Ming; Raiteri, Paolo; Oganov, Artem R.; Pokroy, Boaz; Polishchuk, Iryna; Bygrave, Peter J.; Day, Graeme M.; Rohl, Andrew L.; Tuckerman, Mark; Kahr, Bart.

In: Journal of the American Chemical Society, Vol. 138, No. 14, 27.04.2016, p. 4881-4889.

Research output: Contribution to journalArticle

Zhu, Q, Shtukenberg, AG, Carter, DJ, Yu, TQ, Yang, J, Chen, M, Raiteri, P, Oganov, AR, Pokroy, B, Polishchuk, I, Bygrave, PJ, Day, GM, Rohl, AL, Tuckerman, M & Kahr, B 2016, 'Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles"', Journal of the American Chemical Society, vol. 138, no. 14, pp. 4881-4889. https://doi.org/10.1021/jacs.6b01120
Zhu, Qiang ; Shtukenberg, Alexander G. ; Carter, Damien J. ; Yu, Tang Qing ; Yang, Jingxiang ; Chen, Ming ; Raiteri, Paolo ; Oganov, Artem R. ; Pokroy, Boaz ; Polishchuk, Iryna ; Bygrave, Peter J. ; Day, Graeme M. ; Rohl, Andrew L. ; Tuckerman, Mark ; Kahr, Bart. / Resorcinol Crystallization from the Melt : A New Ambient Phase and New "Riddles". In: Journal of the American Chemical Society. 2016 ; Vol. 138, No. 14. pp. 4881-4889.
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