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

Structures of the a and ß 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 atmospheri...

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Main Authors: Zhu, Q., Shtukenberg, A., Carter, Damien, Yu, T., Yang, J., Chen, M., Raiteri, Paolo, Oganov, A., Pokroy, B., Polishchuk, I., Bygrave, P., Day, G., Rohl, Andrew, Tuckerman, M., Kahr, B.
Format: Journal Article
Published: American Chemical Society 2016
Online Access:http://purl.org/au-research/grants/arc/FT130100463
http://hdl.handle.net/20.500.11937/47672
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author Zhu, Q.
Shtukenberg, A.
Carter, Damien
Yu, T.
Yang, J.
Chen, M.
Raiteri, Paolo
Oganov, A.
Pokroy, B.
Polishchuk, I.
Bygrave, P.
Day, G.
Rohl, Andrew
Tuckerman, M.
Kahr, B.
author_facet Zhu, Q.
Shtukenberg, A.
Carter, Damien
Yu, T.
Yang, J.
Chen, M.
Raiteri, Paolo
Oganov, A.
Pokroy, B.
Polishchuk, I.
Bygrave, P.
Day, G.
Rohl, Andrew
Tuckerman, M.
Kahr, B.
author_sort Zhu, Q.
building Curtin Institutional Repository
collection Online Access
description Structures of the a and ß 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, e, through a combination of optical and X-ray crystallography and by computational crystal structure prediction algorithms. a-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 ß phase. The e phase only grows from the melt, concomitant with the ß 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 ß resorcinol (e, point symmetry 222, does not have a polar axis) with additives that stereoselectively modify growth velocities. Both ß and e 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.
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spelling curtin-20.500.11937-476722019-02-19T05:35:23Z Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles". Zhu, Q. Shtukenberg, A. Carter, Damien Yu, T. Yang, J. Chen, M. Raiteri, Paolo Oganov, A. Pokroy, B. Polishchuk, I. Bygrave, P. Day, G. Rohl, Andrew Tuckerman, M. Kahr, B. Structures of the a and ß 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, e, through a combination of optical and X-ray crystallography and by computational crystal structure prediction algorithms. a-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 ß phase. The e phase only grows from the melt, concomitant with the ß 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 ß resorcinol (e, point symmetry 222, does not have a polar axis) with additives that stereoselectively modify growth velocities. Both ß and e 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. 2016 Journal Article http://hdl.handle.net/20.500.11937/47672 10.1021/jacs.6b01120 http://purl.org/au-research/grants/arc/FT130100463 http://purl.org/au-research/grants/arc/DP140101776 American Chemical Society fulltext
spellingShingle Zhu, Q.
Shtukenberg, A.
Carter, Damien
Yu, T.
Yang, J.
Chen, M.
Raiteri, Paolo
Oganov, A.
Pokroy, B.
Polishchuk, I.
Bygrave, P.
Day, G.
Rohl, Andrew
Tuckerman, M.
Kahr, B.
Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles".
title Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles".
title_full Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles".
title_fullStr Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles".
title_full_unstemmed Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles".
title_short Resorcinol Crystallization from the Melt: A New Ambient Phase and New "Riddles".
title_sort resorcinol crystallization from the melt: a new ambient phase and new "riddles".
url http://purl.org/au-research/grants/arc/FT130100463
http://purl.org/au-research/grants/arc/FT130100463
http://hdl.handle.net/20.500.11937/47672