The study of transitions between polymorphic phases is a less investigated chapter of the widely studied book of polymorphism. In this paper, we discuss the phase behavior of a new compound that has been rationally designed to show frustration of H-bonds for the strong amide N-H donor, which cannot be involved in H-bonding nor in van der Waals interactions. The compound (ImB) is a showcase of almost all possible cases of transitions between polymorphs [monotropic/enantiotropic, fast/slow, diffusive/displacive, and single-crystal-to-single-crystal (SCSC)] and of relation between polymorphs with different Z '. Six crystal phases (I, II, III, IV, V, and VI) were identified for it with five crystal-crystal transitions. Two transitions are reversible/SCSC/fast. Of the three monotropic transitions, all non-SCSC, one is slow, and the others are fast. Of the two enantiotropic SCSC transitions, one does not exhibit undercooling, while the other shows strong undercooling. Phase III, with Z ' = 6, is stable at room temperature between phase II (Z ' = 1), stable at high temperature, and phase IV (Z ' = 2), stable at low temperature. All six polymorphs are based on the same O-HO & boxH;C H-bonding synthon, which produces infinite chains in five polymorphs and ring tetramers in one. The sequence of reversible SCSC transitions IV reversible arrow III reversible arrow II involves a remarkable ping pong of the symmetry rules by which H-bonded chains are built. Based on all of this, a possible roadmap for prediction of SCSC transitions in crystals is shortly outlined.
Frustration of H-Bonding and Frustrated Packings in a Hexamorphic Crystal System with Reversible Crystal–Crystal Transitions / Parisi, Emmanuele; Santagata, Emanuela; Simone, Elena; Borbone, Fabio; Centore, Roberto. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 146:28(2024), pp. 19405-19413. [10.1021/jacs.4c05559]
Frustration of H-Bonding and Frustrated Packings in a Hexamorphic Crystal System with Reversible Crystal–Crystal Transitions
Parisi, Emmanuele;Simone, Elena;
2024
Abstract
The study of transitions between polymorphic phases is a less investigated chapter of the widely studied book of polymorphism. In this paper, we discuss the phase behavior of a new compound that has been rationally designed to show frustration of H-bonds for the strong amide N-H donor, which cannot be involved in H-bonding nor in van der Waals interactions. The compound (ImB) is a showcase of almost all possible cases of transitions between polymorphs [monotropic/enantiotropic, fast/slow, diffusive/displacive, and single-crystal-to-single-crystal (SCSC)] and of relation between polymorphs with different Z '. Six crystal phases (I, II, III, IV, V, and VI) were identified for it with five crystal-crystal transitions. Two transitions are reversible/SCSC/fast. Of the three monotropic transitions, all non-SCSC, one is slow, and the others are fast. Of the two enantiotropic SCSC transitions, one does not exhibit undercooling, while the other shows strong undercooling. Phase III, with Z ' = 6, is stable at room temperature between phase II (Z ' = 1), stable at high temperature, and phase IV (Z ' = 2), stable at low temperature. All six polymorphs are based on the same O-HO & boxH;C H-bonding synthon, which produces infinite chains in five polymorphs and ring tetramers in one. The sequence of reversible SCSC transitions IV reversible arrow III reversible arrow II involves a remarkable ping pong of the symmetry rules by which H-bonded chains are built. Based on all of this, a possible roadmap for prediction of SCSC transitions in crystals is shortly outlined.File | Dimensione | Formato | |
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https://hdl.handle.net/11583/2991496