Thermal single crystal to single crystal transformation among crystal polymorphs in 2-dimethylamino-5,7-bis(trifluoromethyl)-1,8-naphthyridine and in a 1-quinoline analogue

Naomi Harada, Satoru Karasawa, Taisuke Matsumoto, Noboru Koga

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

2-Dimethylamino-5,7-bis(trifluoromethyl)-1,8-naphthyridine 1 was prepared as a new solid-state fluorophore. Recrystallization of 1 from CH 2Cl2/n-hexane afforded three crystal polymorphs, G, BM, and BO, with the space group (crystal class) C2/c (monoclinic), P21/c (monoclinic), and Pbca (orthorhombic), respectively, at 23 C. DSC curves for G showed one endothermic peak at 110 C in the high temperature region and two pairs of endo- and exothermic peaks at ca. 18 and 7 C in the low temperature region, which were assigned as crystal phase transitions. In the high temperature region, a reversible transformation from G to B (a mixture of BM and BO) by heating at 110 C and from B to G by grinding was observed with alteration of the emitted color. In the low temperature region, X-ray crystallography suggested that G transformed to G2 (10 C) and G4 (-50 C) with a subtle alteration of molecular arrangements through thermal single crystal to single crystal interconversion. Eventually, 1 provided five crystal polymorphs, G, G2, G4, BM, and BO, containing eight crystallographically independent molecules. In contrast, the 1-quinoline analogue, 2, provided two crystal polymorphs, 2α (23 C) and 2β (-123 C).

Original languageEnglish
Pages (from-to)4705-4713
Number of pages9
JournalCrystal Growth and Design
Volume13
Issue number11
DOIs
Publication statusPublished - Nov 6 2013

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Naphthyridines
quinoline
Polymorphism
Single crystals
analogs
Crystals
single crystals
crystals
Temperature
Fluorophores
X ray crystallography
Crystal symmetry
Hexane
grinding
Phase transitions
crystallography
Color
Heating
Molecules
Hot Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Thermal single crystal to single crystal transformation among crystal polymorphs in 2-dimethylamino-5,7-bis(trifluoromethyl)-1,8-naphthyridine and in a 1-quinoline analogue. / Harada, Naomi; Karasawa, Satoru; Matsumoto, Taisuke; Koga, Noboru.

In: Crystal Growth and Design, Vol. 13, No. 11, 06.11.2013, p. 4705-4713.

Research output: Contribution to journalArticle

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AB - 2-Dimethylamino-5,7-bis(trifluoromethyl)-1,8-naphthyridine 1 was prepared as a new solid-state fluorophore. Recrystallization of 1 from CH 2Cl2/n-hexane afforded three crystal polymorphs, G, BM, and BO, with the space group (crystal class) C2/c (monoclinic), P21/c (monoclinic), and Pbca (orthorhombic), respectively, at 23 C. DSC curves for G showed one endothermic peak at 110 C in the high temperature region and two pairs of endo- and exothermic peaks at ca. 18 and 7 C in the low temperature region, which were assigned as crystal phase transitions. In the high temperature region, a reversible transformation from G to B (a mixture of BM and BO) by heating at 110 C and from B to G by grinding was observed with alteration of the emitted color. In the low temperature region, X-ray crystallography suggested that G transformed to G2 (10 C) and G4 (-50 C) with a subtle alteration of molecular arrangements through thermal single crystal to single crystal interconversion. Eventually, 1 provided five crystal polymorphs, G, G2, G4, BM, and BO, containing eight crystallographically independent molecules. In contrast, the 1-quinoline analogue, 2, provided two crystal polymorphs, 2α (23 C) and 2β (-123 C).

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