The melting point alternation in α,ω-alkanedithiols

Journal of the American Chemical Society

Volumn 122, Issue 6, 2000, Pages 1186-1190

  Thalladi, Venkat R ^a   Boese, Roland ^a   Weiss, Hans Christoph ^a  

^a UNIVERSITY OF DUISBURG ESSEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANEDIOL DERIVATIVE; THIOL DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; GEOMETRY; HYDROGEN BOND; MELTING POINT; MOLECULAR DYNAMICS; X RAY ANALYSIS;

EID: 0034673356     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993422l     Document Type: Article

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27. The directional preferences of intermolecular interactions of divalent sulfur (excluding thiols) with various other electrophilic or nucleophilic species have been studied. See (a) Rosenfield, R. E.; Parthasarathy, R.; Dunitz, J. D. J. Am. Chem. Soc. 1977, 99, 4860. (b) Row: T. N. G.; Parthasarathy, R. J. Am. Chem. Soc. 1981, 103, 477.
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29. n = 5, 7, and 9) dithiols.
30. Note that we are dealing with S⋯S interactions between SH groups, whereas S⋯S interactions reported in the literature dealt either with thioether or thione functionalities. (See refs 10 and 15b; also (a) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T. Bull. Chem. Soc. Jpn. 1997, 70, 1727. (b) Nyburg, S. C.; Faerman, C. H. Acta Crystallogr. 1985, B41, 274.)
31. Note that we are dealing with S⋯S interactions between SH groups, whereas S⋯S interactions reported in the literature dealt either with thioether or thione functionalities. (See refs 10 and 15b; also (a) Munakata, M.; Wu, L. P.; Kuroda-Sowa, T. Bull. Chem. Soc. Jpn. 1997, 70, 1727. (b) Nyburg, S. C.; Faerman, C. H. Acta Crystallogr. 1985, B41, 274.)
32. Such a reversed offset is observed in the even members of α,ω-alkanediols and α,ω-alkanediamines wherein the end groups control the structure through O-H⋯O and N-H⋯N hydrogen bonds, respectively. (Thalladi, V. R.; Boese, R.; Weiss, H. C. Angew. Chem., Int. Ed. Engl., in press). The fact that dithiols do not follow the packing patterns similar to those of α,ω-alkanediols and α,ω-alkanediamines indicates the reluctance of SH groups to participate in S-H⋯S hydrogen bonding. However, the SH groups in dithiols also form S-H⋯S contacts, but these are long (H⋯ S, 2.94-3.19, S⋯S, 3.91-4.08 Å; and S-H⋯S, 135-154°) and are probably insignificant.
33. k*, Table 1) also show an alternating trend similar to that of densities and melting points.