X-ray study of the hetero ring flexibility in trans-5,6- trimethylene- and tetramethylene-5,6-dihydro 2-phenyl-[4H]-1,3-thiazines

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Abstract

The structures to two 1,3-thiazine derivatives differing only in the number of CH2 groups in their trans fused hydrocarbon ring (n 3 for I and n 4 for II) have been established by X-ray crystallography from diffractometer data. Crystals of I (trans-5,6- trimethylene-5,6-dihydro-2-phenyl-[4H] - 1,3-thiazine) are triclinic, space group P1 with a = 7.661(1), b = 8.282(1), c = 9.566(2) Å, α = 91.75(1), β = 100.72(1), γ 105.45(1)° Z = 2, Dc = 1.260 g cm-3. Crystals of II (trans-5,6-tetramethylene-5,6-dihydro-2-phenyl [4H]-1,3-thiazine) are monoclinic, space group P21/c with a = 7.914(2), b = 19.362(13), c = 8.440(1) Å, β = 109.16(2)°C Z = 4, Dc = 1.258 g cm-3. The structures determined by Patterson (I) and direct (II) methods were refined to R = 0.050 for 1330 reflections of I and R = 0.082 for 1012 reflections of II. The proper treatment of the positional disorder of the carbon atoms (C(5) and C(6)) forming the trans ring junction in I discovered two discrete conformations with a ratio of 1:2. The opposite chirality of atoms C(51) and C(52), and C(61) and C(62), indicates a simultaneous configurational disorder with a pattern of total disorder: AB̄B̄AB̄B̄. The puckering parameters of the hetero rings in the same enantiomers of molecules IA, IB and II indicate a connection between the conformers: 5E(II)→5H6(IB)→E6IA) via pseudorotation. Their relationship is discussed and compared with the conformational freedom of the analogous 1,3-oxazine derivatives.

Original languageEnglish
Pages (from-to)327-337
Number of pages11
JournalJournal of Molecular Structure
Volume140
Issue number3-4
DOIs
Publication statusPublished - 1986

Fingerprint

Thiazines
thiazine (trademark)
flexibility
X-Rays
disorders
Derivatives
X rays
Atoms
Crystals
Enantiomers
Chirality
rings
X ray crystallography
Diffractometers
Oxazines
Conformations
x rays
X Ray Crystallography
Hydrocarbons
enantiomers

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Materials Science (miscellaneous)
  • Atomic and Molecular Physics, and Optics

Cite this

@article{97f90bd946f54ee99b3359c96434590c,
title = "X-ray study of the hetero ring flexibility in trans-5,6- trimethylene- and tetramethylene-5,6-dihydro 2-phenyl-[4H]-1,3-thiazines",
abstract = "The structures to two 1,3-thiazine derivatives differing only in the number of CH2 groups in their trans fused hydrocarbon ring (n 3 for I and n 4 for II) have been established by X-ray crystallography from diffractometer data. Crystals of I (trans-5,6- trimethylene-5,6-dihydro-2-phenyl-[4H] - 1,3-thiazine) are triclinic, space group P1 with a = 7.661(1), b = 8.282(1), c = 9.566(2) {\AA}, α = 91.75(1), β = 100.72(1), γ 105.45(1)° Z = 2, Dc = 1.260 g cm-3. Crystals of II (trans-5,6-tetramethylene-5,6-dihydro-2-phenyl [4H]-1,3-thiazine) are monoclinic, space group P21/c with a = 7.914(2), b = 19.362(13), c = 8.440(1) {\AA}, β = 109.16(2)°C Z = 4, Dc = 1.258 g cm-3. The structures determined by Patterson (I) and direct (II) methods were refined to R = 0.050 for 1330 reflections of I and R = 0.082 for 1012 reflections of II. The proper treatment of the positional disorder of the carbon atoms (C(5) and C(6)) forming the trans ring junction in I discovered two discrete conformations with a ratio of 1:2. The opposite chirality of atoms C(51) and C(52), and C(61) and C(62), indicates a simultaneous configurational disorder with a pattern of total disorder: AB̄B̄AB̄B̄. The puckering parameters of the hetero rings in the same enantiomers of molecules IA, IB and II indicate a connection between the conformers: 5E(II)→5H6(IB)→E6IA) via pseudorotation. Their relationship is discussed and compared with the conformational freedom of the analogous 1,3-oxazine derivatives.",
author = "G. Argay and A. K{\'a}lm{\'a}n and L. Simon and G. Bern{\'a}th",
year = "1986",
doi = "10.1016/0022-2860(86)87015-6",
language = "English",
volume = "140",
pages = "327--337",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",
number = "3-4",

}

TY - JOUR

T1 - X-ray study of the hetero ring flexibility in trans-5,6- trimethylene- and tetramethylene-5,6-dihydro 2-phenyl-[4H]-1,3-thiazines

AU - Argay, G.

AU - Kálmán, A.

AU - Simon, L.

AU - Bernáth, G.

PY - 1986

Y1 - 1986

N2 - The structures to two 1,3-thiazine derivatives differing only in the number of CH2 groups in their trans fused hydrocarbon ring (n 3 for I and n 4 for II) have been established by X-ray crystallography from diffractometer data. Crystals of I (trans-5,6- trimethylene-5,6-dihydro-2-phenyl-[4H] - 1,3-thiazine) are triclinic, space group P1 with a = 7.661(1), b = 8.282(1), c = 9.566(2) Å, α = 91.75(1), β = 100.72(1), γ 105.45(1)° Z = 2, Dc = 1.260 g cm-3. Crystals of II (trans-5,6-tetramethylene-5,6-dihydro-2-phenyl [4H]-1,3-thiazine) are monoclinic, space group P21/c with a = 7.914(2), b = 19.362(13), c = 8.440(1) Å, β = 109.16(2)°C Z = 4, Dc = 1.258 g cm-3. The structures determined by Patterson (I) and direct (II) methods were refined to R = 0.050 for 1330 reflections of I and R = 0.082 for 1012 reflections of II. The proper treatment of the positional disorder of the carbon atoms (C(5) and C(6)) forming the trans ring junction in I discovered two discrete conformations with a ratio of 1:2. The opposite chirality of atoms C(51) and C(52), and C(61) and C(62), indicates a simultaneous configurational disorder with a pattern of total disorder: AB̄B̄AB̄B̄. The puckering parameters of the hetero rings in the same enantiomers of molecules IA, IB and II indicate a connection between the conformers: 5E(II)→5H6(IB)→E6IA) via pseudorotation. Their relationship is discussed and compared with the conformational freedom of the analogous 1,3-oxazine derivatives.

AB - The structures to two 1,3-thiazine derivatives differing only in the number of CH2 groups in their trans fused hydrocarbon ring (n 3 for I and n 4 for II) have been established by X-ray crystallography from diffractometer data. Crystals of I (trans-5,6- trimethylene-5,6-dihydro-2-phenyl-[4H] - 1,3-thiazine) are triclinic, space group P1 with a = 7.661(1), b = 8.282(1), c = 9.566(2) Å, α = 91.75(1), β = 100.72(1), γ 105.45(1)° Z = 2, Dc = 1.260 g cm-3. Crystals of II (trans-5,6-tetramethylene-5,6-dihydro-2-phenyl [4H]-1,3-thiazine) are monoclinic, space group P21/c with a = 7.914(2), b = 19.362(13), c = 8.440(1) Å, β = 109.16(2)°C Z = 4, Dc = 1.258 g cm-3. The structures determined by Patterson (I) and direct (II) methods were refined to R = 0.050 for 1330 reflections of I and R = 0.082 for 1012 reflections of II. The proper treatment of the positional disorder of the carbon atoms (C(5) and C(6)) forming the trans ring junction in I discovered two discrete conformations with a ratio of 1:2. The opposite chirality of atoms C(51) and C(52), and C(61) and C(62), indicates a simultaneous configurational disorder with a pattern of total disorder: AB̄B̄AB̄B̄. The puckering parameters of the hetero rings in the same enantiomers of molecules IA, IB and II indicate a connection between the conformers: 5E(II)→5H6(IB)→E6IA) via pseudorotation. Their relationship is discussed and compared with the conformational freedom of the analogous 1,3-oxazine derivatives.

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JF - Journal of Molecular Structure

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