Different molecular conformations in the crystal structures of three 5-nitroimidazolyl derivatives

Luis F. B. Osorio, Samir A Carvalho, Edson F. da Silva, Carlos A. M. Fraga, Solange M. S. V. Wardell, Bruce F. Milne, James L Wardell, William T A Harrison

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Abstract

The crystal structures of (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-benzyl­oxime, C12H12N4O3, (I), (E)-1-methyl-5-nitro-1H-imidazole-2-carb­alde­hyde O-(4-fluoro­benz­yl) oxime, C12H11FN4O3, (II), and (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-(4-bromo­benz­yl) oxime, C12H11BrN4O3, (III), are described. The dihedral angle between the ring systems in (I) is 49.66 (5)° and the linking Nm—C—C=N (m = methyl­ated) bond shows an anti conformation [torsion angle = 175.00 (15)°]. Compounds (II) and (III) are isostructural [dihedral angle between the aromatic rings = 8.31 (5)° in (II) and 5.34 (15)° in (III)] and differ from (I) in showing a near-syn conformation for the Nm—C—C=N linker [torsion angles for (II) and (III) = 17.64 (18) and 8.7 (5)°, respectively], which allows for the occurrence of a short intra­molecular C—H...N contact. In the crystal of (I), C—H...N hydrogen bonds link the mol­ecules into [010] chains, which are cross-linked by very weak C—H...O bonds into (100) sheets. Weak aromatic π–π stacking inter­actions occur between the sheets. The extended structures of (II) and (III) feature several C—H...N and C—H...O hydrogen bonds, which link the mol­ecules into three-dimensional networks, which are consolidated by aromatic π–π stacking inter­actions. Conformational energy calculations and Hirshfeld fingerprint analyses for (I), (II) and (III) are presented and discussed.
Original languageEnglish
Pages (from-to)380-384
Number of pages5
JournalActa Crystallographica Section E: Structure Reports Online
VolumeE74
Issue number3
Early online date23 Feb 2018
DOIs
Publication statusPublished - 1 Mar 2018

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Dihedral angle
Torsional stress
Conformations
Hydrogen bonds
Oximes
Crystal structure
methylidyne
Derivatives
crystal structure
Molecules
imidazoles
torsion
dihedral angle
Crystals
hydrogen bonds
rings
molecules
imidazole
interactions
occurrences

Keywords

  • benzoxa­thiol-2-one
  • hydrogen bonds
  • Hirshfeld surface
  • crystal structure

Cite this

Different molecular conformations in the crystal structures of three 5-nitroimidazolyl derivatives. / Osorio, Luis F. B. ; Carvalho, Samir A; da Silva, Edson F. ; Fraga, Carlos A. M.; Wardell, Solange M. S. V.; Milne, Bruce F.; Wardell, James L; Harrison, William T A.

In: Acta Crystallographica Section E: Structure Reports Online, Vol. E74, No. 3, 01.03.2018, p. 380-384.

Research output: Contribution to journalArticle

Osorio, Luis F. B. ; Carvalho, Samir A ; da Silva, Edson F. ; Fraga, Carlos A. M. ; Wardell, Solange M. S. V. ; Milne, Bruce F. ; Wardell, James L ; Harrison, William T A. / Different molecular conformations in the crystal structures of three 5-nitroimidazolyl derivatives. In: Acta Crystallographica Section E: Structure Reports Online. 2018 ; Vol. E74, No. 3. pp. 380-384.
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abstract = "The crystal structures of (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-benzyl­oxime, C12H12N4O3, (I), (E)-1-methyl-5-nitro-1H-imidazole-2-carb­alde­hyde O-(4-fluoro­benz­yl) oxime, C12H11FN4O3, (II), and (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-(4-bromo­benz­yl) oxime, C12H11BrN4O3, (III), are described. The dihedral angle between the ring systems in (I) is 49.66 (5)° and the linking Nm—C—C=N (m = methyl­ated) bond shows an anti conformation [torsion angle = 175.00 (15)°]. Compounds (II) and (III) are isostructural [dihedral angle between the aromatic rings = 8.31 (5)° in (II) and 5.34 (15)° in (III)] and differ from (I) in showing a near-syn conformation for the Nm—C—C=N linker [torsion angles for (II) and (III) = 17.64 (18) and 8.7 (5)°, respectively], which allows for the occurrence of a short intra­molecular C—H...N contact. In the crystal of (I), C—H...N hydrogen bonds link the mol­ecules into [010] chains, which are cross-linked by very weak C—H...O bonds into (100) sheets. Weak aromatic π–π stacking inter­actions occur between the sheets. The extended structures of (II) and (III) feature several C—H...N and C—H...O hydrogen bonds, which link the mol­ecules into three-dimensional networks, which are consolidated by aromatic π–π stacking inter­actions. Conformational energy calculations and Hirshfeld fingerprint analyses for (I), (II) and (III) are presented and discussed.",
keywords = "benzoxa­thiol-2-one, hydrogen bonds, Hirshfeld surface, crystal structure",
author = "Osorio, {Luis F. B.} and Carvalho, {Samir A} and {da Silva}, {Edson F.} and Fraga, {Carlos A. M.} and Wardell, {Solange M. S. V.} and Milne, {Bruce F.} and Wardell, {James L} and Harrison, {William T A}",
note = "Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the X-ray data collections.",
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T1 - Different molecular conformations in the crystal structures of three 5-nitroimidazolyl derivatives

AU - Osorio, Luis F. B.

AU - Carvalho, Samir A

AU - da Silva, Edson F.

AU - Fraga, Carlos A. M.

AU - Wardell, Solange M. S. V.

AU - Milne, Bruce F.

AU - Wardell, James L

AU - Harrison, William T A

N1 - Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the X-ray data collections.

PY - 2018/3/1

Y1 - 2018/3/1

N2 - The crystal structures of (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-benzyl­oxime, C12H12N4O3, (I), (E)-1-methyl-5-nitro-1H-imidazole-2-carb­alde­hyde O-(4-fluoro­benz­yl) oxime, C12H11FN4O3, (II), and (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-(4-bromo­benz­yl) oxime, C12H11BrN4O3, (III), are described. The dihedral angle between the ring systems in (I) is 49.66 (5)° and the linking Nm—C—C=N (m = methyl­ated) bond shows an anti conformation [torsion angle = 175.00 (15)°]. Compounds (II) and (III) are isostructural [dihedral angle between the aromatic rings = 8.31 (5)° in (II) and 5.34 (15)° in (III)] and differ from (I) in showing a near-syn conformation for the Nm—C—C=N linker [torsion angles for (II) and (III) = 17.64 (18) and 8.7 (5)°, respectively], which allows for the occurrence of a short intra­molecular C—H...N contact. In the crystal of (I), C—H...N hydrogen bonds link the mol­ecules into [010] chains, which are cross-linked by very weak C—H...O bonds into (100) sheets. Weak aromatic π–π stacking inter­actions occur between the sheets. The extended structures of (II) and (III) feature several C—H...N and C—H...O hydrogen bonds, which link the mol­ecules into three-dimensional networks, which are consolidated by aromatic π–π stacking inter­actions. Conformational energy calculations and Hirshfeld fingerprint analyses for (I), (II) and (III) are presented and discussed.

AB - The crystal structures of (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-benzyl­oxime, C12H12N4O3, (I), (E)-1-methyl-5-nitro-1H-imidazole-2-carb­alde­hyde O-(4-fluoro­benz­yl) oxime, C12H11FN4O3, (II), and (E)-1-methyl-5-nitro-1H-imidazole-2-carbaldehyde O-(4-bromo­benz­yl) oxime, C12H11BrN4O3, (III), are described. The dihedral angle between the ring systems in (I) is 49.66 (5)° and the linking Nm—C—C=N (m = methyl­ated) bond shows an anti conformation [torsion angle = 175.00 (15)°]. Compounds (II) and (III) are isostructural [dihedral angle between the aromatic rings = 8.31 (5)° in (II) and 5.34 (15)° in (III)] and differ from (I) in showing a near-syn conformation for the Nm—C—C=N linker [torsion angles for (II) and (III) = 17.64 (18) and 8.7 (5)°, respectively], which allows for the occurrence of a short intra­molecular C—H...N contact. In the crystal of (I), C—H...N hydrogen bonds link the mol­ecules into [010] chains, which are cross-linked by very weak C—H...O bonds into (100) sheets. Weak aromatic π–π stacking inter­actions occur between the sheets. The extended structures of (II) and (III) feature several C—H...N and C—H...O hydrogen bonds, which link the mol­ecules into three-dimensional networks, which are consolidated by aromatic π–π stacking inter­actions. Conformational energy calculations and Hirshfeld fingerprint analyses for (I), (II) and (III) are presented and discussed.

KW - benzoxa­thiol-2-one

KW - hydrogen bonds

KW - Hirshfeld surface

KW - crystal structure

U2 - 10.1107/S2056989018002876

DO - 10.1107/S2056989018002876

M3 - Article

VL - E74

SP - 380

EP - 384

JO - Acta Crystallographica Section E: Structure Reports Online

JF - Acta Crystallographica Section E: Structure Reports Online

SN - 1600-5368

IS - 3

ER -