Unusual Saddle-like Structure of (2-MeOC6H4CS)2S: Theoretical Studies and Comparison with its Oxygen Isologues

Authors

  • Osamu Niyomura,

    1. Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501–1193, Japan, # Present address: Maruno-uchi 2–14–32, Lions-City Maruno-uchi 1105, Naka-ku, Nagoya 460–0002, Japan
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  • Yuka Kito,

    1. Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501–1193, Japan, # Present address: Maruno-uchi 2–14–32, Lions-City Maruno-uchi 1105, Naka-ku, Nagoya 460–0002, Japan
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  • Shinzi Kato,

    Corresponding author
    1. Department of Applied Chemistry, College of Engineering, Chubu University, Kasugai 487–8501, Japan
    • Department of Applied Chemistry, College of Engineering, Chubu University, Kasugai 487–8501, Japan, Fax: +81-52-222-2442
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  • Masaru Ishida,

    1. Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501–1193, Japan, # Present address: Maruno-uchi 2–14–32, Lions-City Maruno-uchi 1105, Naka-ku, Nagoya 460–0002, Japan
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  • Masahiro Ebihara,

    1. Department of Chemistry, Faculty of Engineering, Gifu University, Gifu 501–1193, Japan, # Present address: Maruno-uchi 2–14–32, Lions-City Maruno-uchi 1105, Naka-ku, Nagoya 460–0002, Japan
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  • Satoko Hayashi,

    1. Department of Material Science, Faculty of Systems Engineering and Chemistry, Wakayama University, Wakayama, 650–8510, Japan
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  • Waro Nakanishi

    Corresponding author
    1. Department of Material Science, Faculty of Systems Engineering and Chemistry, Wakayama University, Wakayama, 650–8510, Japan
    • Department of Material Science, Faculty of Systems Engineering and Chemistry, Wakayama University, Wakayama, 650–8510, Japan
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  • Supporting Information for this article is available on the WWW under http://dx.doi.org/10.1002/zaac.201200357 or from the author.

Abstract

Compound (2-MeOC6H4CS)2S (1) showed an unusual saddle structure in which the –C(=S)–S–C(=S)– moiety is planar and two benzene rings lie a face-to-face and the distances (3.07 Å) between the central sulfur atom and two 2-methoxy oxygen atoms are within the sum of van der Waals radii of the both atoms. However, the results of MO calculation at the B3LYP/6-311+G(2d, p) level showed no orbital interaction between both atoms. From the results of the calculations at the MP2 level, it was deduced that the crystal packing effect is important for such densely packed crystal, due to its less effective volume. On the other hand, the para-methoxy derivative (4-MeOC6H4CS)2S (2) in which the two methoxy oxygen atoms are not able to contact with the central sulfur atom shows an L-shaped structure in which the –C(=S)–S–C(=S)– moiety is not planar. The –C(=O)–S–C(=S)– moiety in compound (2-MeOC6H4CO)(2-MeOC6H4CS)S (3b) shows an L-shaped structure, though the two methoxy oxygen atoms are in intramolecular contact with the central sulfur atom. The deep blue to green colors of compounds 1 and 2 and the deep violet color of compound 3b are due to transitions of the lone-pair electrons in the HOMO (ψ87) of the thiocarbonyl sulfur atom to the LUMO (ψ89)and of those in the HOMO (ψ83) of the thiocarbonyl sulfur atom to the LUMO (ψ85), respectively.

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