Journal of Thermal Analysis and Calorimetry

, Volume 90, Issue 1, pp 39–47 | Cite as

Role of structural and macrocrystalline factors in the desolvation behaviour of cortisone acetate solvates



A combined analysis of structural data and experimental results (DSC, temperature-resolved XRPD and hot stage optical microscopy) revealed that the dehydration mechanism of cortisone acetate monohydrate (CTA·H2O) involves a collective and anisotropic departure of water molecules followed by a cooperative structural reorganization toward the anhydrous polymorph CTA (form 2). In spite of the lack of crystal structure data, it can be postulated from experimental data that thermal decomposition of the dihydrated form (CTA·2H2O) and of the tetrahydrofuran solvate (CTA·THF) toward another polymorph (CTA (form 3)) also proceeds according to a cooperative mechanism, thus giving rise to probable structural filiations between these crystalline forms of CTA. The crystal structure determination of two original solvates (CTA·DMF and CTA·DMSO) indicates that these phases are isomorphous to the previously reported acetone solvate. However, their desolvation behaviour does not involve a cooperative mechanism, as could be expected from structural data only. Instead, the decomposition mechanism of CTA·DMF and CTA·DMSO starts with the formation of a solvent-proof superficial layer, followed by the partial dissolution of the enclosed inner part of crystals.

Hot stage optical microscopy observations and DSC measurements showed that dissolved materials (resulting from a peritectic decomposition) is suddenly evacuated through macroscopic cracks about 30°C above the ebullition point of each solvent. From this unusual behaviour, the necessity to investigate rigorously the various aspects (thermodynamics, kinetics, crystal structures and physical factors) of solvate decompositions is highlighted, including factors related to the particular preparation route of each sample.


crystal structure desolvation mechanism solid-solid transformation solvates 


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Copyright information

© Springer Science+Business Media, LLC. 2007

Authors and Affiliations

  • S. Petit
    • 1
  • F. Mallet
    • 1
  • M. -N. Petit
    • 1
  • G. Coquerel
    • 1
  1. 1.Unité de Croissance Cristalline et de Modélisation Moléculaire (UC2M2), Sciences et Méthodes Séparatives (SMS) UPRES EA 3233, IRCOFUniversité de RouenMont Saint-Aignan CedexFrance

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