Phenol and Toluene Stacking Interactions, Including Interactions at Large Horizontal Displacements. Study of Crystal Structures and Calculation of Potential Energy Surfaces
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The study of crystal structures from the Cambridge Structural Database (CSD) shows that most of p-phenol/p-phenol and toluene/toluene stacking interactions are at large horizontal displacements (offsets) as well as benzene/benzene interactions. The interactions at large horizontal displacements are stabilized by the addition of simultaneous interactions in supramolecular structures in crystals. The stacking p-phenol/p-phenol tends to be orientated in a parallel and antiparallel fashion, while stacking toluene/toluene is almost all in an antiparallel orientation. It is in accordance with calculated interaction energies. Namely, the strongest interaction energies for parallel and antiparallel phenol/phenol dimers are −5.12 and −4.40 kcal/mol, at offsets of 1.5 and 3.0 Å, respectively, while for parallel and antiparallel toluene/toluene dimers, energies are −3.98 and −5.39 kcal/mol, at offsets of 3.0 Å. These interactions are stronger than benzene/benzene stacking (−2.85 kcal/mol), as a c...onsequence of the presence of the substituents. Similar to benzene/benzene stacking, interactions for phenol/phenol and toluene/toluene stacking at large offsets (4.0 Å) can be strong, stronger than −2.0 kcal/mol.
Source:Crystal Growth & Design, 2020, 20, 2, 1025-1034
- American Chemical Society
- Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3979