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Synthesis, X‐ray Diffraction and Computational Study of the Crystal Packing of Polycyclic Hydrocarbons Featuring Aromatic and Perfluoroaromatic Rings Condensed in the Same Molecule: 1,2,3,4‐Tetrafluoronaphthalene, ‐anthracene and ‐phenanthrene
Author(s) -
Cozzi Franco,
Bacchi Sergio,
Filippini Giuseppe,
Pilati Tullio,
Gavezzotti Angelo
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700267
Subject(s) - anthracene , phenanthrene , aromaticity , chemistry , crystallography , molecule , crystal (programming language) , planar , stack (abstract data type) , organic chemistry , programming language , computer graphics (images) , computer science
We have synthesised some planar polycyclic compounds, in which unsubstituted aromatic rings are condensed with perfluorinated aromatic rings, and have carried out a combined X‐ray diffraction and computational study to analyse their self‐recognition behaviour in crystalline phases. We compare our results with the parent hydrocarbons and with other compounds that have a variable degree of fluorination. Whereas the molecular planes in crystals of hydrocarbons with mono‐ or difluorinated aromatic rings or of perfluorinated compounds arrange themselves in V‐shaped configurations, our present results show that perfluorinated rings tend to stack over unsubstituted rings even when these two moieties coexist in a condensed system, producing crystalline materials with parallel molecular layers with the arene–perfluoroarene recognition pattern. Our analysis shows that the packing energy of all these crystals is dispersion‐dominated and that coulombic terms are selective rather than quantitatively predominant in crystals with arene–perfluoroarene interactions. No compelling proof of a special role of CH⋅⋅⋅F interactions has been found.