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Cross-nucleation between ROY polymorphs.

Shuang Chen1, Hanmi Xi, Lian Yu

  • 1School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA.

Journal of the American Chemical Society
|December 8, 2005
PubMed
Summary
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Cross-nucleation between crystal polymorphs challenges existing crystallization theories. This study reveals how different polymorphs can induce each other

Area of Science:

  • Crystallization Science
  • Materials Science
  • Physical Chemistry

Background:

  • Crystal polymorphism, the ability of a solid material to exist in multiple crystal forms, is crucial in pharmaceuticals and materials science.
  • Existing theories like Ostwald's law of stages do not fully explain crystallization pathways in complex polymorphic systems.
  • The phenomenon of cross-nucleation between polymorphs has only recently been recognized as a significant factor.

Purpose of the Study:

  • To investigate the phenomenon of cross-nucleation in the melt crystallization of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY), a highly polymorphic compound.
  • To understand how cross-nucleation influences the crystallization pathway and the formation of new polymorphs.
  • To identify factors affecting cross-nucleation, such as temperature and seed crystal surface properties.

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Main Methods:

  • Spontaneous and seeded melt crystallization experiments were performed on the ROY system.
  • Systematic observation and characterization of crystal polymorph formation and interconversion.
  • Analysis of the thermodynamic stability and growth rates of different ROY polymorphs.

Main Results:

  • Extensive and selective cross-nucleation between ROY polymorphs was observed.
  • Certain ROY polymorphs required cross-nucleation for their formation.
  • A new metastable polymorph (the 10th known) of ROY was identified.
  • The growth rate of new polymorphs was found to be faster than or equal to that of the initial polymorph.
  • Cross-nucleation was influenced by temperature and seed crystal surface characteristics.

Conclusions:

  • Cross-nucleation is a critical phenomenon that significantly impacts crystallization pathways in polymorphic systems.
  • Crystallization pathways are determined not only by initial nucleation but also by polymorph-polymorph interactions and differential growth rates.
  • This study expands the understanding of crystal polymorphism and provides insights into controlling crystal form development.