Spontaneous resolution and crystal structure of (2 S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4 H -1,3-thiazin-4-one; Crystal structure of rac -2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4 H -1,3-thiazin-4-one

Hemant P. Yennawar, Heather G. Bradley, Kristen C. Perhonitch, Haley E. Reppert, Lee J. Silverberg

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Abstract

The crystal structures of isomeric rac-2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (1) and (2S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (2) are reported here. While 1 crystallizes in a centrosymmetric space group, the crystal of 2 chosen for data collection has molecules only with (2S) chirality. This is the result of spontaneous resolution during crystallization, as the synthesis produces a racemic mixture. A crystal with (2R) molecules was also found in the same crystallization vial (structure factors available). The six-membered thiazine ring in both 1 and 2 displays an envelope conformation with the S atom forming the flap. The aryl rings in both structures adopt an approximate V shape with angles between their planes of 46.97(14)° in 1 and 58.37(10)° in 2. In both structures, the molecules form layers in the ab plane. Within such a layer in 1, one of the O atoms of the nitrophenyl group accepts a C - H...O hydrogen bond from the CH group at position 5 of the thiazine ring of a molecule of opposite chirality, forming chains along the a-axis direction. Each of the thiazine rings also participate in C - H...O bonds with the same carbon atom as above, resulting in chains along the b-axis direction, albeit of monochiral type. Adjacent layers are consolidated along the c-axis direction by pairs of parallel hydrogen bonds (C - H...O type) between the nitrophenyl groups of enantiomers. In 2, the two C - H...O hydrogen bonds contribute to chain formation along the b-axis direction. Weak edge-to-face interactions between the aryl groups of neighbouring molecules in 1, and C - H...π interactions between a thiazine ring CH group and a phenyl group of a neighboring molecule in 2 are also observed.

Original languageEnglish (US)
Pages (from-to)454-457
Number of pages4
JournalActa Crystallographica Section E: Crystallographic Communications
Volume74
DOIs
StatePublished - Apr 1 2018

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Thiazines
thiazine (trademark)
Crystal structure
crystal structure
Molecules
Hydrogen bonds
rings
Chirality
molecules
Crystallization
Atoms
hydrogen bonds
chirality
Crystals
methylidyne
crystallization
Enantiomers
atoms
enantiomers
Conformations

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

@article{4d5ba7b6ef2a4ac9aa6af87d7cd4dccb,
title = "Spontaneous resolution and crystal structure of (2 S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4 H -1,3-thiazin-4-one; Crystal structure of rac -2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4 H -1,3-thiazin-4-one",
abstract = "The crystal structures of isomeric rac-2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (1) and (2S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (2) are reported here. While 1 crystallizes in a centrosymmetric space group, the crystal of 2 chosen for data collection has molecules only with (2S) chirality. This is the result of spontaneous resolution during crystallization, as the synthesis produces a racemic mixture. A crystal with (2R) molecules was also found in the same crystallization vial (structure factors available). The six-membered thiazine ring in both 1 and 2 displays an envelope conformation with the S atom forming the flap. The aryl rings in both structures adopt an approximate V shape with angles between their planes of 46.97(14)° in 1 and 58.37(10)° in 2. In both structures, the molecules form layers in the ab plane. Within such a layer in 1, one of the O atoms of the nitrophenyl group accepts a C - H...O hydrogen bond from the CH group at position 5 of the thiazine ring of a molecule of opposite chirality, forming chains along the a-axis direction. Each of the thiazine rings also participate in C - H...O bonds with the same carbon atom as above, resulting in chains along the b-axis direction, albeit of monochiral type. Adjacent layers are consolidated along the c-axis direction by pairs of parallel hydrogen bonds (C - H...O type) between the nitrophenyl groups of enantiomers. In 2, the two C - H...O hydrogen bonds contribute to chain formation along the b-axis direction. Weak edge-to-face interactions between the aryl groups of neighbouring molecules in 1, and C - H...π interactions between a thiazine ring CH group and a phenyl group of a neighboring molecule in 2 are also observed.",
author = "Yennawar, {Hemant P.} and Bradley, {Heather G.} and Perhonitch, {Kristen C.} and Reppert, {Haley E.} and Silverberg, {Lee J.}",
year = "2018",
month = "4",
day = "1",
doi = "10.1107/S2056989018003444",
language = "English (US)",
volume = "74",
pages = "454--457",
journal = "Acta Crystallographica Section E: Crystallographic Communications",
issn = "2056-9890",
publisher = "International Union of Crystallography",

}

TY - JOUR

T1 - Spontaneous resolution and crystal structure of (2 S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4 H -1,3-thiazin-4-one; Crystal structure of rac -2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4 H -1,3-thiazin-4-one

AU - Yennawar, Hemant P.

AU - Bradley, Heather G.

AU - Perhonitch, Kristen C.

AU - Reppert, Haley E.

AU - Silverberg, Lee J.

PY - 2018/4/1

Y1 - 2018/4/1

N2 - The crystal structures of isomeric rac-2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (1) and (2S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (2) are reported here. While 1 crystallizes in a centrosymmetric space group, the crystal of 2 chosen for data collection has molecules only with (2S) chirality. This is the result of spontaneous resolution during crystallization, as the synthesis produces a racemic mixture. A crystal with (2R) molecules was also found in the same crystallization vial (structure factors available). The six-membered thiazine ring in both 1 and 2 displays an envelope conformation with the S atom forming the flap. The aryl rings in both structures adopt an approximate V shape with angles between their planes of 46.97(14)° in 1 and 58.37(10)° in 2. In both structures, the molecules form layers in the ab plane. Within such a layer in 1, one of the O atoms of the nitrophenyl group accepts a C - H...O hydrogen bond from the CH group at position 5 of the thiazine ring of a molecule of opposite chirality, forming chains along the a-axis direction. Each of the thiazine rings also participate in C - H...O bonds with the same carbon atom as above, resulting in chains along the b-axis direction, albeit of monochiral type. Adjacent layers are consolidated along the c-axis direction by pairs of parallel hydrogen bonds (C - H...O type) between the nitrophenyl groups of enantiomers. In 2, the two C - H...O hydrogen bonds contribute to chain formation along the b-axis direction. Weak edge-to-face interactions between the aryl groups of neighbouring molecules in 1, and C - H...π interactions between a thiazine ring CH group and a phenyl group of a neighboring molecule in 2 are also observed.

AB - The crystal structures of isomeric rac-2-(4-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (1) and (2S)-2-(3-nitrophenyl)-3-phenyl-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one (C16 H14 N2 O3 S) (2) are reported here. While 1 crystallizes in a centrosymmetric space group, the crystal of 2 chosen for data collection has molecules only with (2S) chirality. This is the result of spontaneous resolution during crystallization, as the synthesis produces a racemic mixture. A crystal with (2R) molecules was also found in the same crystallization vial (structure factors available). The six-membered thiazine ring in both 1 and 2 displays an envelope conformation with the S atom forming the flap. The aryl rings in both structures adopt an approximate V shape with angles between their planes of 46.97(14)° in 1 and 58.37(10)° in 2. In both structures, the molecules form layers in the ab plane. Within such a layer in 1, one of the O atoms of the nitrophenyl group accepts a C - H...O hydrogen bond from the CH group at position 5 of the thiazine ring of a molecule of opposite chirality, forming chains along the a-axis direction. Each of the thiazine rings also participate in C - H...O bonds with the same carbon atom as above, resulting in chains along the b-axis direction, albeit of monochiral type. Adjacent layers are consolidated along the c-axis direction by pairs of parallel hydrogen bonds (C - H...O type) between the nitrophenyl groups of enantiomers. In 2, the two C - H...O hydrogen bonds contribute to chain formation along the b-axis direction. Weak edge-to-face interactions between the aryl groups of neighbouring molecules in 1, and C - H...π interactions between a thiazine ring CH group and a phenyl group of a neighboring molecule in 2 are also observed.

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JO - Acta Crystallographica Section E: Crystallographic Communications

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