Recurrent Supramolecular Motifs in a Series of Acid-Base Adducts Based on Pyridine-2,5-Dicarboxylic Acid N -Oxide and Organic Bases: Inter- and Intramolecular Hydrogen Bonding

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dc.contributor.author Mirzaei, M.
dc.contributor.author Sadeghi, F.
dc.contributor.author Molčanov,K.
dc.contributor.author Zarȩba, J. K.
dc.contributor.author Gomila, R.M.
dc.contributor.author Frontera, A.
dc.date.accessioned 2024-02-09T09:00:18Z
dc.date.available 2024-02-09T09:00:18Z
dc.identifier.uri http://hdl.handle.net/11201/164675
dc.description.abstract [eng] Single-crystal to single-crystal polymorphic transformations in molecular solids are relatively rare, with changes in crystal structure more commonly leading to destruction of the parent crystal. However, the structural basis for such transitions is of considerable interest given the changes in material properties that can result. The antihistamine desloratadine displays a two-step, reversible single-crystal to single-crystal phase transition during heating/cooling cycles between three conformational polymorphs: the low temperature form I, a polytypic intermediate form II, and the high temperature form III. The two-step transition involves a sequential flipping of the piperidine rings of desloratadine molecules in the crystals, which induce reversible micrometer-scale contraction on heating and expansion on cooling of the largest face of a desloratadine single crystal. Distinct, slow-moving phase boundaries, originating on the (001) face of the crystal, were observed sweeping through the entire crystal in hot-stage microscopy, suggesting a single nucleation event. Computational spectroscopy, using periodic DFT-D phonon calculations, reproduces the experimental variable-temperatureTHz-Raman spectra and rules out the possibility of the phase transformations occurring via any classical soft mode. A combination of variable-temperature powder X-ray diffraction, solid-state NMR, and computational spectroscopy provides a detailed molecular description of the phase transitions, indicating a first-order diffusionless process between I → II and II → III, wherein both conformational changes and lattice distortions occur simultaneously in the crystal lattice. The study indicates that a nucleation and growth mechanism is compatible with concerted movements producing a conformational change in organic molecular crystals.
dc.format application/pdf
dc.relation.isformatof Versió postprint del document publicat a: https://doi.org/10.1021/acs.cgd.9b01475
dc.relation.ispartof Crystal Growth & Design, 2020, vol. 20, num. 3, p. 1738-1751
dc.subject.classification 54 - Química
dc.subject.other 54 - Chemistry. Crystallography. Mineralogy
dc.title Recurrent Supramolecular Motifs in a Series of Acid-Base Adducts Based on Pyridine-2,5-Dicarboxylic Acid N -Oxide and Organic Bases: Inter- and Intramolecular Hydrogen Bonding
dc.type info:eu-repo/semantics/article
dc.type info:eu-repo/semantics/acceptedVersion
dc.date.updated 2024-02-09T09:00:20Z
dc.rights.accessRights info:eu-repo/semantics/openAccess
dc.identifier.doi https://doi.org/10.1021/acs.cgd.9b01475


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