[en] Phenoxazine is a heterocyclic molecule, which is used either as a parent molecule or with substituents for applications in various scientific fields: e.g., as a potential antioxidant. The purpose of this work is to present the molecular packing of phenoxazine within the crystalline state, as surprisingly no crystal structure is known so far. The crystal structure solution was performed by single-crystal X-ray investigations. Although the molecule has some potential for intermolecular hydrogen bonding, the observed structure is the classical herringbone packing typical for rodlike conjugated molecules. However, severe substitutional disorder of oxygen and nitrogen atoms is observed over their two opposite positions within the molecule. To get deeper insight into this disorder phenomenon, theoretical studies were performed, including crystal structure prediction using state of the art density functional theory techniques. The theoretical investigations confirm the experimentally observed 50% occupancy of the oxygen and nitrogen atoms.
Disciplines :
Chemistry
Author, co-author :
Kaltenegger, Martin; Laboratoire de Chimie des Polymères, Faculté des Sciences, Université Libre de Bruxelles (ULB), Cp, Bruxelles, Belgium ; Institute of Solid State Physics, University of Technology Graz, Graz, Austria
Delaive, Louis; Laboratory for Chemistry of Novel Materials, Materials Research Institute, University of Mons, Mons, Belgium
Gali, Sai Manoj ; Laboratory for Chemistry of Novel Materials, Materials Research Institute, University of Mons, Mons, Belgium
Brocorens, Patrick ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Werzer, Oliver; Department for Pharmaceutical Technology and Biopharmacy, Institute Pharmaceutical Sciences, Graz University, Graz, Austria
Riegler, Hans; Department for Pharmaceutical Technology and Biopharmacy, Institute Pharmaceutical Sciences, Graz University, Graz, Austria
Geerts, Yves Henri ; Laboratoire de Chimie des Polymères, Faculté des Sciences, Université Libre de Bruxelles (ULB), Cp, Bruxelles, Belgium ; International Solvay Institutes of Physics and Chemistry, Brussels, Belgium
Lazzaroni, Roberto ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Resel, Roland ; Institute of Solid State Physics, University of Technology Graz, Graz, Austria
Liu, Jie ; Laboratoire de Chimie des Polymères, Faculté des Sciences, Université Libre de Bruxelles (ULB), Cp, Bruxelles, Belgium
Language :
English
Title :
Molecular Packing of Phenoxazine: A Combined Single-Crystal/Crystal Structure Prediction Study
F?d?ration Wallonie-Bruxelles Universit? Libre de Bruxelles Fonds De La Recherche Scientifique - FNRS
Funding text :
The financial support of the Belgian National Fund for Scientific Research (FNRS) for the projects Phasetrans no. T.0058.14, Pi-Fast no. T.0072.18, and EOS 2Dto3D no. 30489208 is gratefully acknowledged. Financial support from the ULB and the French Community of Belgium (ARC SADI) is also gratefully acknowledged. We thank the synchrotron radiation facility Elettra, Trieste, Italy, for support in using the beamline XRD1. The molecular modeling activities were supported by the FNRS (Consortium des Équipements de Calcul Intensif-CÉCI, under Grant 2.5020.11) and by the Walloon Region (ZENOBE Tier-1 supercomputer, under grant 1117545).
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