1. Critical Influence of Water on the Polymorphism of 1,3-Dimethylurea and Other Heterogeneous Equilibria
- Author
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Grace Baaklini, Manon Schindler, Lina Yuan, Clément De Saint Jores, Morgane Sanselme, Nicolas Couvrat, Simon Clevers, Philippe Négrier, Denise Mondieig, Valérie Dupray, Yohann Cartigny, Gabin Gbabode, and Gerard Coquerel
- Subjects
phase diagrams ,polymorphism ,hydrate ,phase transitions ,crystal structure determination ,Organic chemistry ,QD241-441 - Abstract
It is shown that the presence of hundreds of ppm of water in 1,3-dimethylurea (DMU) powder led to the large depression of the transition temperature between the two enantiotropically related polymorphic forms of DMU (Form II → Form I) from 58 °C to 25 °C, thus explaining the reported discrepancies on this temperature of transition. Importantly, this case study shows that thermodynamics (through the construction of the DMU–water temperature-composition phase diagram) rather than kinetics is responsible for this significant temperature drop. Furthermore, this work also highlights the existence of a monohydrate of DMU that has never been reported before with a non-congruent fusion at 8 °C. Interestingly, its crystal structure, determined from X-ray powder diffraction data at sub-ambient temperature, consists of a DMU–water hydrogen bonded network totally excluding homo-molecular hydrogen bonds (whereas present in forms I and II of DMU).
- Published
- 2023
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