Co-crystal of (R,R)-1,2-cyclohexanediol with (R,R)-tartaric acid, a key structure in resolution of the (±)-trans-diol by supercritical extraction, and the related ternary phase system

Paul Thorey, P. Bombicz, Imre Miklós Szilágyi, Péter Molnár, György Bánsághi, Edit Székely, B. Simándi, L. Párkányí, G. Pokol, J. Madarász

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

A novel co-crystal of trans-(R,R)-1,2-cyclohexanediol and (R,R)-tartaric acid (with 1:1 molar ratio, 1) has been found to be a key crystalline compound in the improved resolution of (±)-trans-1,2-cyclohexanediol by supercritical fluid extraction. The molecular and crystal structure of this co-crystal, which crystallizes in orthorhombic crystal system (space group P212121, a = 6.7033(13) Å, b = 7.2643(16), c = 24.863(5), Z = 4), has been solved by single crystal X-ray diffraction (R = 0.064). The packing arrangement consists of two dimensional layers of sandwich-like sheets, where the inner part is constructed by double layers of tartaric acids which hydrophilicity is "covered" on both upper and bottom side by cyclohexanediols with the hydrophobic cyclohexane rings pointing outward. Thus, a rather complex hydrogen bonding pattern is constructed. The relatively high melting point (133 °C) observed by both simultaneous TG/DTA and DSC, and the main features of FTIR-spectrum of 1 are explained by the increased stability of this crystal structure. DSC studies on binary mixtures of co-crystal 1 with (R,R)-1,2-cyclohexanediol or (R,R)-tartaric acid, revealed eutectic temperatures of Teu = 100 or 131 °C, respectively. Between (S,S)-1,2-cyclohexanediol and (R,R)-tartaric acid a eutectic temperature of Teu = 85 °C have also been observed. The phase relations have been confirmed by powder X-ray diffraction, as well.

Original languageEnglish
Pages (from-to)129-136
Number of pages8
JournalThermochimica Acta
Volume497
Issue number1-2
DOIs
Publication statusPublished - Jan 10 2010

Fingerprint

Crystals
acids
Acids
eutectics
Eutectics
crystals
Crystal structure
crystal structure
Supercritical fluids
supercritical fluids
Hydrophilicity
Cyclohexane
Binary mixtures
diffraction
cyclohexane
X ray powder diffraction
Differential thermal analysis
Molecular structure
binary mixtures
melting points

Keywords

  • (±)-Trans-1,2-cyclohexanediol
  • (R,R)-Tartaric acid
  • Binary melting phase diagrams
  • Chiral resolution
  • Crystal structure determination
  • Differential scanning calorimetry (DSC)
  • Eutectic compositions and temperatures
  • FTIR spectroscopy
  • Simultaneous TG/DTA
  • Single crystal and powder X-ray diffraction (XRD)
  • Structure-property relationship

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Condensed Matter Physics
  • Instrumentation

Cite this

Co-crystal of (R,R)-1,2-cyclohexanediol with (R,R)-tartaric acid, a key structure in resolution of the (±)-trans-diol by supercritical extraction, and the related ternary phase system. / Thorey, Paul; Bombicz, P.; Szilágyi, Imre Miklós; Molnár, Péter; Bánsághi, György; Székely, Edit; Simándi, B.; Párkányí, L.; Pokol, G.; Madarász, J.

In: Thermochimica Acta, Vol. 497, No. 1-2, 10.01.2010, p. 129-136.

Research output: Contribution to journalArticle

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abstract = "A novel co-crystal of trans-(R,R)-1,2-cyclohexanediol and (R,R)-tartaric acid (with 1:1 molar ratio, 1) has been found to be a key crystalline compound in the improved resolution of (±)-trans-1,2-cyclohexanediol by supercritical fluid extraction. The molecular and crystal structure of this co-crystal, which crystallizes in orthorhombic crystal system (space group P212121, a = 6.7033(13) {\AA}, b = 7.2643(16), c = 24.863(5), Z = 4), has been solved by single crystal X-ray diffraction (R = 0.064). The packing arrangement consists of two dimensional layers of sandwich-like sheets, where the inner part is constructed by double layers of tartaric acids which hydrophilicity is {"}covered{"} on both upper and bottom side by cyclohexanediols with the hydrophobic cyclohexane rings pointing outward. Thus, a rather complex hydrogen bonding pattern is constructed. The relatively high melting point (133 °C) observed by both simultaneous TG/DTA and DSC, and the main features of FTIR-spectrum of 1 are explained by the increased stability of this crystal structure. DSC studies on binary mixtures of co-crystal 1 with (R,R)-1,2-cyclohexanediol or (R,R)-tartaric acid, revealed eutectic temperatures of Teu = 100 or 131 °C, respectively. Between (S,S)-1,2-cyclohexanediol and (R,R)-tartaric acid a eutectic temperature of Teu = 85 °C have also been observed. The phase relations have been confirmed by powder X-ray diffraction, as well.",
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AU - Thorey, Paul

AU - Bombicz, P.

AU - Szilágyi, Imre Miklós

AU - Molnár, Péter

AU - Bánsághi, György

AU - Székely, Edit

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AU - Párkányí, L.

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N2 - A novel co-crystal of trans-(R,R)-1,2-cyclohexanediol and (R,R)-tartaric acid (with 1:1 molar ratio, 1) has been found to be a key crystalline compound in the improved resolution of (±)-trans-1,2-cyclohexanediol by supercritical fluid extraction. The molecular and crystal structure of this co-crystal, which crystallizes in orthorhombic crystal system (space group P212121, a = 6.7033(13) Å, b = 7.2643(16), c = 24.863(5), Z = 4), has been solved by single crystal X-ray diffraction (R = 0.064). The packing arrangement consists of two dimensional layers of sandwich-like sheets, where the inner part is constructed by double layers of tartaric acids which hydrophilicity is "covered" on both upper and bottom side by cyclohexanediols with the hydrophobic cyclohexane rings pointing outward. Thus, a rather complex hydrogen bonding pattern is constructed. The relatively high melting point (133 °C) observed by both simultaneous TG/DTA and DSC, and the main features of FTIR-spectrum of 1 are explained by the increased stability of this crystal structure. DSC studies on binary mixtures of co-crystal 1 with (R,R)-1,2-cyclohexanediol or (R,R)-tartaric acid, revealed eutectic temperatures of Teu = 100 or 131 °C, respectively. Between (S,S)-1,2-cyclohexanediol and (R,R)-tartaric acid a eutectic temperature of Teu = 85 °C have also been observed. The phase relations have been confirmed by powder X-ray diffraction, as well.

AB - A novel co-crystal of trans-(R,R)-1,2-cyclohexanediol and (R,R)-tartaric acid (with 1:1 molar ratio, 1) has been found to be a key crystalline compound in the improved resolution of (±)-trans-1,2-cyclohexanediol by supercritical fluid extraction. The molecular and crystal structure of this co-crystal, which crystallizes in orthorhombic crystal system (space group P212121, a = 6.7033(13) Å, b = 7.2643(16), c = 24.863(5), Z = 4), has been solved by single crystal X-ray diffraction (R = 0.064). The packing arrangement consists of two dimensional layers of sandwich-like sheets, where the inner part is constructed by double layers of tartaric acids which hydrophilicity is "covered" on both upper and bottom side by cyclohexanediols with the hydrophobic cyclohexane rings pointing outward. Thus, a rather complex hydrogen bonding pattern is constructed. The relatively high melting point (133 °C) observed by both simultaneous TG/DTA and DSC, and the main features of FTIR-spectrum of 1 are explained by the increased stability of this crystal structure. DSC studies on binary mixtures of co-crystal 1 with (R,R)-1,2-cyclohexanediol or (R,R)-tartaric acid, revealed eutectic temperatures of Teu = 100 or 131 °C, respectively. Between (S,S)-1,2-cyclohexanediol and (R,R)-tartaric acid a eutectic temperature of Teu = 85 °C have also been observed. The phase relations have been confirmed by powder X-ray diffraction, as well.

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KW - Eutectic compositions and temperatures

KW - FTIR spectroscopy

KW - Simultaneous TG/DTA

KW - Single crystal and powder X-ray diffraction (XRD)

KW - Structure-property relationship

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