Hypervalent S-Cl bond in cyclic acylaminochloro-λ4-sulfanes

A comparison of N-S-Cl, N-S+ClO4/- and N-S+···O=C bond systems

D. Szabó, István Kapovits, Árpád Kucsman, Péter Nagy, G. Argay, A. Kálmán

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Two cyclic acylaminochloro-λ4-sulfanes containing a five- or a six- membered hetero ring (5 and 6), as well as their cyclic acylaminosulfonium salt analogues without (7 and 8) and with S···O close contact (9 and 10), have been prepared and their molecular structures determined by X-ray diffraction. Compounds 5, 6, 9 and 10 exhibit a trigonal bipyramidal configuration about the central sulfur atom, with nitrogen and chlorine (in 5 and 6) or with nitrogen and oxygen atoms (in 9 and 10) in axial positions. In sulfonium salts 7 and 8, the bond angles about sulfur are similar to those obtained for analogous λ4-sulfanes 5 and 6. The interatomic S-N distances, which range from 1.66 to 1.73 Å point to a strong covalent bond in all compounds investigated. In λ4-sulfanes the axial S-Cl hypervalent bond (2.69 Å in 5, 3.10 Å in 6) is rather long and markedly polarized. In methoxycarbonyl-substituted acylaminosulfonium salts the interatomic S···O distances are 2.41 Å (in 9) and 2.74 Å (in 10). The individual S-N, S-Cl, S···O and S-C(ar) bond lengths, as well as the N(ax)-S-X(ax) (X = Cl or O=), N(ax)-S-C(ar)(eq), Cl(ax)-S-C(ar)(eq) and C(ar)(eq)- S-C(ar)'(eq) bond angles (159-176°, 90-104°, 85-96°and 101-104°, respectively), which depend on both the axial substituents on sulfur and the size of the hetero ring, are compared and discussed. The five-membered 2,3-dihydro-isothiazole rings in 5, 7 and 9 are practically planar, whereas the 1,2-oxathiole 'ring' in 10 is unusually puckered. The six-membered dihydro-1,2-thiazine rings in 6, 8 and 10, as well as the 1,2-oxathiine 'ring' in 9, assume a more or less inverted half-chair form. The orientations of the aromatic rings in relation to the C(ar)(eq)-S-C(ar)'(eq) plane are also discussed.

Original languageEnglish
Pages (from-to)157-171
Number of pages15
JournalJournal of Molecular Structure
Volume476
Issue number1-3
DOIs
Publication statusPublished - Feb 23 1999

Fingerprint

Sulfur
Salts
Oxathiins
rings
Nitrogen
Thiazines
Atoms
Covalent bonds
Chlorine
Bond length
sulfur
Molecular Structure
X-Ray Diffraction
Molecular structure
salts
Oxygen
thiazine (trademark)
X ray diffraction
covalent bonds
perchlorate

Keywords

  • Chloro-λ-sulfanes
  • Hypervalent bonds
  • Sulfonium salts
  • Sulfur-oxygen interaction

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Hypervalent S-Cl bond in cyclic acylaminochloro-λ4-sulfanes : A comparison of N-S-Cl, N-S+ClO4/- and N-S+···O=C bond systems. / Szabó, D.; Kapovits, István; Kucsman, Árpád; Nagy, Péter; Argay, G.; Kálmán, A.

In: Journal of Molecular Structure, Vol. 476, No. 1-3, 23.02.1999, p. 157-171.

Research output: Contribution to journalArticle

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title = "Hypervalent S-Cl bond in cyclic acylaminochloro-λ4-sulfanes: A comparison of N-S-Cl, N-S+ClO4/- and N-S+···O=C bond systems",
abstract = "Two cyclic acylaminochloro-λ4-sulfanes containing a five- or a six- membered hetero ring (5 and 6), as well as their cyclic acylaminosulfonium salt analogues without (7 and 8) and with S···O close contact (9 and 10), have been prepared and their molecular structures determined by X-ray diffraction. Compounds 5, 6, 9 and 10 exhibit a trigonal bipyramidal configuration about the central sulfur atom, with nitrogen and chlorine (in 5 and 6) or with nitrogen and oxygen atoms (in 9 and 10) in axial positions. In sulfonium salts 7 and 8, the bond angles about sulfur are similar to those obtained for analogous λ4-sulfanes 5 and 6. The interatomic S-N distances, which range from 1.66 to 1.73 {\AA} point to a strong covalent bond in all compounds investigated. In λ4-sulfanes the axial S-Cl hypervalent bond (2.69 {\AA} in 5, 3.10 {\AA} in 6) is rather long and markedly polarized. In methoxycarbonyl-substituted acylaminosulfonium salts the interatomic S···O distances are 2.41 {\AA} (in 9) and 2.74 {\AA} (in 10). The individual S-N, S-Cl, S···O and S-C(ar) bond lengths, as well as the N(ax)-S-X(ax) (X = Cl or O=), N(ax)-S-C(ar)(eq), Cl(ax)-S-C(ar)(eq) and C(ar)(eq)- S-C(ar)'(eq) bond angles (159-176°, 90-104°, 85-96°and 101-104°, respectively), which depend on both the axial substituents on sulfur and the size of the hetero ring, are compared and discussed. The five-membered 2,3-dihydro-isothiazole rings in 5, 7 and 9 are practically planar, whereas the 1,2-oxathiole 'ring' in 10 is unusually puckered. The six-membered dihydro-1,2-thiazine rings in 6, 8 and 10, as well as the 1,2-oxathiine 'ring' in 9, assume a more or less inverted half-chair form. The orientations of the aromatic rings in relation to the C(ar)(eq)-S-C(ar)'(eq) plane are also discussed.",
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AU - Szabó, D.

AU - Kapovits, István

AU - Kucsman, Árpád

AU - Nagy, Péter

AU - Argay, G.

AU - Kálmán, A.

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N2 - Two cyclic acylaminochloro-λ4-sulfanes containing a five- or a six- membered hetero ring (5 and 6), as well as their cyclic acylaminosulfonium salt analogues without (7 and 8) and with S···O close contact (9 and 10), have been prepared and their molecular structures determined by X-ray diffraction. Compounds 5, 6, 9 and 10 exhibit a trigonal bipyramidal configuration about the central sulfur atom, with nitrogen and chlorine (in 5 and 6) or with nitrogen and oxygen atoms (in 9 and 10) in axial positions. In sulfonium salts 7 and 8, the bond angles about sulfur are similar to those obtained for analogous λ4-sulfanes 5 and 6. The interatomic S-N distances, which range from 1.66 to 1.73 Å point to a strong covalent bond in all compounds investigated. In λ4-sulfanes the axial S-Cl hypervalent bond (2.69 Å in 5, 3.10 Å in 6) is rather long and markedly polarized. In methoxycarbonyl-substituted acylaminosulfonium salts the interatomic S···O distances are 2.41 Å (in 9) and 2.74 Å (in 10). The individual S-N, S-Cl, S···O and S-C(ar) bond lengths, as well as the N(ax)-S-X(ax) (X = Cl or O=), N(ax)-S-C(ar)(eq), Cl(ax)-S-C(ar)(eq) and C(ar)(eq)- S-C(ar)'(eq) bond angles (159-176°, 90-104°, 85-96°and 101-104°, respectively), which depend on both the axial substituents on sulfur and the size of the hetero ring, are compared and discussed. The five-membered 2,3-dihydro-isothiazole rings in 5, 7 and 9 are practically planar, whereas the 1,2-oxathiole 'ring' in 10 is unusually puckered. The six-membered dihydro-1,2-thiazine rings in 6, 8 and 10, as well as the 1,2-oxathiine 'ring' in 9, assume a more or less inverted half-chair form. The orientations of the aromatic rings in relation to the C(ar)(eq)-S-C(ar)'(eq) plane are also discussed.

AB - Two cyclic acylaminochloro-λ4-sulfanes containing a five- or a six- membered hetero ring (5 and 6), as well as their cyclic acylaminosulfonium salt analogues without (7 and 8) and with S···O close contact (9 and 10), have been prepared and their molecular structures determined by X-ray diffraction. Compounds 5, 6, 9 and 10 exhibit a trigonal bipyramidal configuration about the central sulfur atom, with nitrogen and chlorine (in 5 and 6) or with nitrogen and oxygen atoms (in 9 and 10) in axial positions. In sulfonium salts 7 and 8, the bond angles about sulfur are similar to those obtained for analogous λ4-sulfanes 5 and 6. The interatomic S-N distances, which range from 1.66 to 1.73 Å point to a strong covalent bond in all compounds investigated. In λ4-sulfanes the axial S-Cl hypervalent bond (2.69 Å in 5, 3.10 Å in 6) is rather long and markedly polarized. In methoxycarbonyl-substituted acylaminosulfonium salts the interatomic S···O distances are 2.41 Å (in 9) and 2.74 Å (in 10). The individual S-N, S-Cl, S···O and S-C(ar) bond lengths, as well as the N(ax)-S-X(ax) (X = Cl or O=), N(ax)-S-C(ar)(eq), Cl(ax)-S-C(ar)(eq) and C(ar)(eq)- S-C(ar)'(eq) bond angles (159-176°, 90-104°, 85-96°and 101-104°, respectively), which depend on both the axial substituents on sulfur and the size of the hetero ring, are compared and discussed. The five-membered 2,3-dihydro-isothiazole rings in 5, 7 and 9 are practically planar, whereas the 1,2-oxathiole 'ring' in 10 is unusually puckered. The six-membered dihydro-1,2-thiazine rings in 6, 8 and 10, as well as the 1,2-oxathiine 'ring' in 9, assume a more or less inverted half-chair form. The orientations of the aromatic rings in relation to the C(ar)(eq)-S-C(ar)'(eq) plane are also discussed.

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KW - Sulfonium salts

KW - Sulfur-oxygen interaction

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