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Order-disorder twinning model and stacking faults in alpha-NTO.

Dieter Schwarzenbach1, Kristin Kirschbaum, A Alan Pinkerton

  • 1Laboratoire de Cristallographie, Ecole Polytechnique Fédérale, Le Cubotron, CH-1015 Lausanne, Switzerland. dieter.schwarzenbach@epfl.ch

Acta Crystallographica. Section B, Structural Science
|September 20, 2006
PubMed
Summary

The triclinic structure of 5-nitro-2,4-dihydro-1,2,4-triazol-3-one (alpha-NTO) exhibits fourfold twinning due to stacking faults. This phenomenon is explained by layer stacking and local symmetry, offering insights into crystal structure and order-disorder phenomena.

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Area of Science:

  • Crystallography
  • Materials Science
  • Solid State Chemistry

Background:

  • The triclinic structure of 5-nitro-2,4-dihydro-1,2,4-triazol-3-one (alpha-NTO) was recently determined.
  • Crystals of alpha-NTO exhibit complex fourfold twinning.
  • The asymmetric unit contains Z' = 4 independent molecules.

Purpose of the Study:

  • To investigate the origin of the fourfold twinning in alpha-NTO crystals.
  • To explain the presence of multiple independent molecules (Z'=4) in the asymmetric unit.
  • To apply order-disorder theory to understand the observed crystal structure.

Main Methods:

  • Analysis of the published crystal structure of alpha-NTO.
  • Application of layer group symmetry concepts.
  • Utilizing order-disorder theory and local symmetry operations.
  • Identification of ordered structures and common reflections.

Main Results:

  • The alpha-NTO structure features layers with p2(1)/b 1 (1) symmetry.
  • Stacking of these layers leads to the loss of overall symmetry and explains Z'=4.
  • Twinning arises from stacking faults, with layers adopting four equivalent positions.
  • Near-neighbor molecular relationships are preserved across twin boundaries.
  • Four maximally ordered structures and their common reflections were identified.

Conclusions:

  • Stacking faults in layered structures are a primary cause of twinning in alpha-NTO.
  • Order-disorder theory provides a framework for understanding the twinning and multiple independent molecules.
  • The study elucidates the relationship between local symmetry, stacking, and macroscopic crystal properties.