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Role of halogen substituents in a series of polymorphic 2,5-diamino-3,6-dicyanopyrazine derivatives with highly flexible groups

  • Yoko Akune , Risa Hirosawa , Atsushi Koseki and Shinya Matsumoto EMAIL logo
Published/Copyright: February 7, 2017
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 232 Issue 5

Abstract

The crystal structures of the ortho-X-benzyl derivatives, where X=F, Cl, Br, I, and Me, of 2,5-bis(N,N-dibenzylamino)-3,6-dicyanopyrazine dyes (C34H24N6X4) were analysed to evaluate the effect of a systematic series of structures on the occurrence of polymorphism. Detailed crystal structure analysis indicated that the thermally stable forms of the polymorphic derivatives (Cl and Br derivatives) were close-packed, whereas those of the non-polymorphic derivatives (F and I derivatives) were stabilised by an intermolecular interaction involving the ortho-substituents. In the thermally metastable forms of the polymorphic derivative, halogen-halogen and halogen-nitrogen interactions contributed to the stabilisation of these crystals in the same way as the thermally stable form of the non-polymorphic derivatives. This indicated that the ease of polymorph occurrence would require an appropriate balance between the crystal energy of the close-packed structure and that of the crystal structure generated mainly by the electrostatic interactions involving the halogens in these halogenated pyrazine derivatives. In addition, the similar tendency of the occurrence of polymorphs in these halogenated pyrazine derivatives was found in 19 sets of halogenated compounds having known crystal structures of F, Cl, Br and I derivatives including at least one polymorphic derivative in the crystal structure database.

Keywords: conformational polymorphism; conformational potential surface; halogen bonding; substituent effect; 2,5-diamino-3,6-dicyanopyrazine

Acknowledgements

The authors thank Dr Mitsuhiro Yanagita of Nippon Soda Co. Ltd. for the kind provision of some of the dye samples. The study was supported by the joint research project “Subject C” of the Research Institute of Environment and Information Sciences of Yokohama National University.

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Supplemental Material:

The online version of this article (DOI: 10.1515/zkri-2016-2007) offers supplementary material, available to authorized users.

Received: 2016-9-15
Accepted: 2017-1-5
Published Online: 2017-2-7
Published in Print: 2017-5-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Obituary
  4. Howard David Flack (1943–2017)
  5. Inorganic Crystal Structures
  6. Crystal structures of [SbF6]− salts of di- and tetrahydrated Ag +, tetrahydrated Pd2 + and hexahydrated Cd2 + cations
  7. The novel stairs-like layered compound Co5(OH)6(H2O)2[SO3]2
  8. A “missing” caesium member in the family of A3Al2P3O12 aluminophosphates
  9. Ternary gallides RE4Rh9Ga5, RE5Rh12Ga7 and RE7Rh18Ga11 (RE=Y, La–Nd, Sm, Gd, Tb) – intergrowth structures with MgCu2 and CaCu5 related slabs
  10. Organic and Metalorganic Crystal Structures
  11. OD- and non-OD-polytypism of 9-(3-chloropyridin-4-yl)-9H-carbazole
  12. Two mefenamic acid derivatives: structural study using powder X-ray diffraction, Hirshfeld surface and molecular electrostatic potential calculations
  13. Role of halogen substituents in a series of polymorphic 2,5-diamino-3,6-dicyanopyrazine derivatives with highly flexible groups
https://doi.org/10.1515/zkri-2016-2007
Keywords for this article
conformational polymorphism; conformational potential surface; halogen bonding; substituent effect; 2,5-diamino-3,6-dicyanopyrazine

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Obituary
  4. Howard David Flack (1943–2017)
  5. Inorganic Crystal Structures
  6. Crystal structures of [SbF6]− salts of di- and tetrahydrated Ag +, tetrahydrated Pd2 + and hexahydrated Cd2 + cations
  7. The novel stairs-like layered compound Co5(OH)6(H2O)2[SO3]2
  8. A “missing” caesium member in the family of A3Al2P3O12 aluminophosphates
  9. Ternary gallides RE4Rh9Ga5, RE5Rh12Ga7 and RE7Rh18Ga11 (RE=Y, La–Nd, Sm, Gd, Tb) – intergrowth structures with MgCu2 and CaCu5 related slabs
  10. Organic and Metalorganic Crystal Structures
  11. OD- and non-OD-polytypism of 9-(3-chloropyridin-4-yl)-9H-carbazole
  12. Two mefenamic acid derivatives: structural study using powder X-ray diffraction, Hirshfeld surface and molecular electrostatic potential calculations
  13. Role of halogen substituents in a series of polymorphic 2,5-diamino-3,6-dicyanopyrazine derivatives with highly flexible groups
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