Transannular sulfur-nitrogen interaction in 1,5-thiazocine derivatives

An x-ray study

M. Kuti, J. Rábai, I. Kapovits, I. Jalsovszky, G. Argay, A. Kálmán, L. Párkányí

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

7-Acetylbenzo[b]naphtho[1,8-f,g]thiazocin-8(7H)-one(sulfide- N- acetyllactam 3) and its 13-oxide (sulfoxide-N-acetyllactam 4, exhibiting polymorphy, 4a and 4b) have been prepared and their structures established by X-ray crystallography from diffractometer data. Compound 3 (C19H13NO2S) crystallizes in the monoclinic space group P21/c with a = 10.716(3), b = 9.222(2), c= 16.077(5) Å,β = 106.68(2)°, V = 1521.9(7) Å, Z = 4, D(c) = 1.394g cm-3 and μ(Mo Kα) = 0.22 mm-1. Compound 4a (C19H13No3S) crystallizes in the monoclinic space group Pc with a 7.821(1), b = 24.795(6), c = 8.342(1) Å,β = 101.15(1)°, V = 1587.2(4) Å3, Z = 4 (two molecules, 4a' and 4a, in the asymmetric unit), D(c) = 1.40 g cm-3 and μ(Mo Kα) = 0.21 mm-1. Compound 4b also crystallizes in the monoclinic space group P21/c with a = 11.791(1),b = 10.719(1),c = 25.193(2) Å,β = 96.02(1)°, V = 3166.4(4) Å3, Z = 8 (two molecules, 4b' and 4b' in the asymmetric unit), D(c) = 1.394 g cm-3 and μ(Cu Kα) = 1.92 mm-1. The crystal structures were solved by direct methods and refined to R = 0.052 for 3, R = 0.088 for 4a, and R = 0.048 for 4b, by using 9413, 4759 and 5195 reflections, respectively. Owing to the cis-amide structure, compounds 3 and 4 assume a boat-like conformation with transannular sulfur- nitrogen close contact; r(S ··· N) = 2.968(1) Å for 3 and 2.753(3)- 2.832(2) Å for 4a' and 4b. The out-of-ring position of the sulfinyl oxygen leads to a sulfurane-like trigonal bipyramidal geometry about sulfur in 4a' and 4b'; Θ(O = S ··· N) = 175.8(3)178.7(2)°. The interatomic distances r(S = O) = 1.483(2) 1.498(3) Å and r(O=S ··· N) = 4.245 4.314 Å are in agreement with an S=O double bond and S ··· N close contact rather than with an O S N type molecular structure observed in spirosulfuranes. The stereochemistries of 1,5-thiazocine and 1,5-thiazonine rings are compared.

Original languageEnglish
Pages (from-to)1-11
Number of pages11
JournalJournal of Molecular Structure
Volume382
Issue number1
DOIs
Publication statusPublished - Aug 15 1996

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Dilatation and Curettage
sulfoxide
Sulfur
Nitrogen
sulfur
X-Rays
Derivatives
nitrogen
X rays
Stereochemistry
Molecules
X ray crystallography
Diffractometers
Boats
Sulfides
Amides
Oxides
Molecular structure
Conformations
x rays

Keywords

  • 1,5-Thiazocine derivative
  • Conformational isomerism
  • Transannular sulphur-nitrogen interaction
  • X-ray crystallography

ASJC Scopus subject areas

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

Cite this

Transannular sulfur-nitrogen interaction in 1,5-thiazocine derivatives : An x-ray study. / Kuti, M.; Rábai, J.; Kapovits, I.; Jalsovszky, I.; Argay, G.; Kálmán, A.; Párkányí, L.

In: Journal of Molecular Structure, Vol. 382, No. 1, 15.08.1996, p. 1-11.

Research output: Contribution to journalArticle

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title = "Transannular sulfur-nitrogen interaction in 1,5-thiazocine derivatives: An x-ray study",
abstract = "7-Acetylbenzo[b]naphtho[1,8-f,g]thiazocin-8(7H)-one(sulfide- N- acetyllactam 3) and its 13-oxide (sulfoxide-N-acetyllactam 4, exhibiting polymorphy, 4a and 4b) have been prepared and their structures established by X-ray crystallography from diffractometer data. Compound 3 (C19H13NO2S) crystallizes in the monoclinic space group P21/c with a = 10.716(3), b = 9.222(2), c= 16.077(5) {\AA},β = 106.68(2)°, V = 1521.9(7) {\AA}, Z = 4, D(c) = 1.394g cm-3 and μ(Mo Kα) = 0.22 mm-1. Compound 4a (C19H13No3S) crystallizes in the monoclinic space group Pc with a 7.821(1), b = 24.795(6), c = 8.342(1) {\AA},β = 101.15(1)°, V = 1587.2(4) {\AA}3, Z = 4 (two molecules, 4a' and 4a, in the asymmetric unit), D(c) = 1.40 g cm-3 and μ(Mo Kα) = 0.21 mm-1. Compound 4b also crystallizes in the monoclinic space group P21/c with a = 11.791(1),b = 10.719(1),c = 25.193(2) {\AA},β = 96.02(1)°, V = 3166.4(4) {\AA}3, Z = 8 (two molecules, 4b' and 4b' in the asymmetric unit), D(c) = 1.394 g cm-3 and μ(Cu Kα) = 1.92 mm-1. The crystal structures were solved by direct methods and refined to R = 0.052 for 3, R = 0.088 for 4a, and R = 0.048 for 4b, by using 9413, 4759 and 5195 reflections, respectively. Owing to the cis-amide structure, compounds 3 and 4 assume a boat-like conformation with transannular sulfur- nitrogen close contact; r(S ··· N) = 2.968(1) {\AA} for 3 and 2.753(3)- 2.832(2) {\AA} for 4a' and 4b. The out-of-ring position of the sulfinyl oxygen leads to a sulfurane-like trigonal bipyramidal geometry about sulfur in 4a' and 4b'; Θ(O = S ··· N) = 175.8(3)178.7(2)°. The interatomic distances r(S = O) = 1.483(2) 1.498(3) {\AA} and r(O=S ··· N) = 4.245 4.314 {\AA} are in agreement with an S=O double bond and S ··· N close contact rather than with an O S N type molecular structure observed in spirosulfuranes. The stereochemistries of 1,5-thiazocine and 1,5-thiazonine rings are compared.",
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T1 - Transannular sulfur-nitrogen interaction in 1,5-thiazocine derivatives

T2 - An x-ray study

AU - Kuti, M.

AU - Rábai, J.

AU - Kapovits, I.

AU - Jalsovszky, I.

AU - Argay, G.

AU - Kálmán, A.

AU - Párkányí, L.

PY - 1996/8/15

Y1 - 1996/8/15

N2 - 7-Acetylbenzo[b]naphtho[1,8-f,g]thiazocin-8(7H)-one(sulfide- N- acetyllactam 3) and its 13-oxide (sulfoxide-N-acetyllactam 4, exhibiting polymorphy, 4a and 4b) have been prepared and their structures established by X-ray crystallography from diffractometer data. Compound 3 (C19H13NO2S) crystallizes in the monoclinic space group P21/c with a = 10.716(3), b = 9.222(2), c= 16.077(5) Å,β = 106.68(2)°, V = 1521.9(7) Å, Z = 4, D(c) = 1.394g cm-3 and μ(Mo Kα) = 0.22 mm-1. Compound 4a (C19H13No3S) crystallizes in the monoclinic space group Pc with a 7.821(1), b = 24.795(6), c = 8.342(1) Å,β = 101.15(1)°, V = 1587.2(4) Å3, Z = 4 (two molecules, 4a' and 4a, in the asymmetric unit), D(c) = 1.40 g cm-3 and μ(Mo Kα) = 0.21 mm-1. Compound 4b also crystallizes in the monoclinic space group P21/c with a = 11.791(1),b = 10.719(1),c = 25.193(2) Å,β = 96.02(1)°, V = 3166.4(4) Å3, Z = 8 (two molecules, 4b' and 4b' in the asymmetric unit), D(c) = 1.394 g cm-3 and μ(Cu Kα) = 1.92 mm-1. The crystal structures were solved by direct methods and refined to R = 0.052 for 3, R = 0.088 for 4a, and R = 0.048 for 4b, by using 9413, 4759 and 5195 reflections, respectively. Owing to the cis-amide structure, compounds 3 and 4 assume a boat-like conformation with transannular sulfur- nitrogen close contact; r(S ··· N) = 2.968(1) Å for 3 and 2.753(3)- 2.832(2) Å for 4a' and 4b. The out-of-ring position of the sulfinyl oxygen leads to a sulfurane-like trigonal bipyramidal geometry about sulfur in 4a' and 4b'; Θ(O = S ··· N) = 175.8(3)178.7(2)°. The interatomic distances r(S = O) = 1.483(2) 1.498(3) Å and r(O=S ··· N) = 4.245 4.314 Å are in agreement with an S=O double bond and S ··· N close contact rather than with an O S N type molecular structure observed in spirosulfuranes. The stereochemistries of 1,5-thiazocine and 1,5-thiazonine rings are compared.

AB - 7-Acetylbenzo[b]naphtho[1,8-f,g]thiazocin-8(7H)-one(sulfide- N- acetyllactam 3) and its 13-oxide (sulfoxide-N-acetyllactam 4, exhibiting polymorphy, 4a and 4b) have been prepared and their structures established by X-ray crystallography from diffractometer data. Compound 3 (C19H13NO2S) crystallizes in the monoclinic space group P21/c with a = 10.716(3), b = 9.222(2), c= 16.077(5) Å,β = 106.68(2)°, V = 1521.9(7) Å, Z = 4, D(c) = 1.394g cm-3 and μ(Mo Kα) = 0.22 mm-1. Compound 4a (C19H13No3S) crystallizes in the monoclinic space group Pc with a 7.821(1), b = 24.795(6), c = 8.342(1) Å,β = 101.15(1)°, V = 1587.2(4) Å3, Z = 4 (two molecules, 4a' and 4a, in the asymmetric unit), D(c) = 1.40 g cm-3 and μ(Mo Kα) = 0.21 mm-1. Compound 4b also crystallizes in the monoclinic space group P21/c with a = 11.791(1),b = 10.719(1),c = 25.193(2) Å,β = 96.02(1)°, V = 3166.4(4) Å3, Z = 8 (two molecules, 4b' and 4b' in the asymmetric unit), D(c) = 1.394 g cm-3 and μ(Cu Kα) = 1.92 mm-1. The crystal structures were solved by direct methods and refined to R = 0.052 for 3, R = 0.088 for 4a, and R = 0.048 for 4b, by using 9413, 4759 and 5195 reflections, respectively. Owing to the cis-amide structure, compounds 3 and 4 assume a boat-like conformation with transannular sulfur- nitrogen close contact; r(S ··· N) = 2.968(1) Å for 3 and 2.753(3)- 2.832(2) Å for 4a' and 4b. The out-of-ring position of the sulfinyl oxygen leads to a sulfurane-like trigonal bipyramidal geometry about sulfur in 4a' and 4b'; Θ(O = S ··· N) = 175.8(3)178.7(2)°. The interatomic distances r(S = O) = 1.483(2) 1.498(3) Å and r(O=S ··· N) = 4.245 4.314 Å are in agreement with an S=O double bond and S ··· N close contact rather than with an O S N type molecular structure observed in spirosulfuranes. The stereochemistries of 1,5-thiazocine and 1,5-thiazonine rings are compared.

KW - 1,5-Thiazocine derivative

KW - Conformational isomerism

KW - Transannular sulphur-nitrogen interaction

KW - X-ray crystallography

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