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Two Modifications Formed by “Sulflower” C16S8 Molecules, Their Study by XRD and Optical Spectroscopy (Raman, IR, UV−Vis) Methods

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A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova street, 119991 Moscow, Russia, Department of Chemistry, Moscow State University, Leninskiye Gory, 119992 Moscow, Russia, and Department of Natural Sciences, New Mexico Highlands University, Las Vegas, New Mexico 87701
* Corresponding author. E-mail: [email protected]
†A. N. Nesmeyanov Institute of Organelement Compounds, Russian Academy of Sciences.
‡Moscow State University.
§New Mexico Highlands University.
Cite this: J. Phys. Chem. A 2008, 112, 43, 10949–10961
Publication Date (Web):October 7, 2008
https://doi.org/10.1021/jp806134u
Copyright © 2008 American Chemical Society
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Abstract

Sublimation of sulflower, octathio[8]circulene C16S8 (1), on heating under high vacuum (∼10−5 Torr) leads to successive formation of two modifications: a white film (1W) and a red polycrystalline solid (1R). When kept at room temperature for several weeks, 1W spontaneously turns pink, reflecting the monotropic phase transition 1W → 1R. The accurate molecular and crystal structure of 1R has been studied using low-temperature (100 K) high-resolution single crystal X-ray analysis. The C16S8 molecule in crystal is strictly planar with nearly equalized bonds of each type (C−C, C−S, and C═C). The point symmetry group of the free molecule is D8h, and the crystal space group is P21/n. These data allowed group-theoretical analysis of vibrational normal modes to be accomplished. Investigation of the charge density distribution of 1R including Bader’s AIM approach has revealed rather strong intermolecular S···S, S···C, and C···C interactions of charge transfer and π-stacking types with overall lattice energy of 28.5 kcal/mol. The charge transfer due to the S···S interactions is the reason for the red coloration of 1R. The latter is reflected by its UV−vis spectrum exhibiting absorption bands in the visible region which are absent from that of 1W. Both modifications were studied comparatively by vibrational (Raman, IR) and electronic spectroscopies as well as XRD powder diffraction. All the results obtained are fully consistent and show that 1W is much less ordered than 1R with significantly weakened intermolecular interactions. Rationalizing of these results has led to an idea that 1W could be soluble, in contrast to 1R. Indeed, 1W appeared soluble in common solvents; this finding opens the way to the study of the chemistry of 1 and investigation of its electrooptical properties.

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Tables giving bond lengths and angles, topological parameters in critical points (3,−1), atomic charges, and volumes, parameters of selected diffraction peaks in the powder XRD patterns, and detailed analysis of the vibrational spectrum on the basis of computed and experimental data are presented. This material is available free of charge via the Internet at http://pubs.acs.org. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary no. CCDC-685932. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ U.K. (Fax: (international) +44-1223/336-033; E-mail: deposit @ccdc.cam.ac.uk).

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