(E)-1-(Pyridin-2-yl)ethanone O-acryloyloxime

Mariusz Mojzych; Zbigniew Karczmarzyk; Andrzej Fruziński

doi:10.1107/S1600536808005436

. 2008 Mar 5;64(Pt 4):o653. doi: 10.1107/S1600536808005436

(E)-1-(Pyridin-2-yl)ethanone O-acryloyloxime

Mariusz Mojzych ^a,^*, Zbigniew Karczmarzyk ^a, Andrzej Fruziński ^b

PMCID: PMC2961001 PMID: 21202050

Abstract

The title compound, C₁₀H₁₀N₂O₂, was synthesized by the reaction of the oxime of 2-acetylpyridine and 3-bromopropanoyl chloride in the presence of triethylamine. The molecule adopts a nearly planar chain-extended conformation with the oxime group in a trans and the acryloyl group in an s-cis conformation. This conformation is stabilized by an intramolecular C—H⋯N hydrogen bond. The screw-related molecules are linked into C(9) chains by C—H⋯O hydrogen bonds.

Related literature

For general background, see: Robertson, (1995 ▶). For the biological activity of oximes, see: Van Helden et al. (1996 ▶). For related structures, see: Mojzych et al. (2007 ▶). For the graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₀N₂O₂
M _r = 190.20
Monoclinic,
a = 7.0240 (5) Å
b = 18.4054 (14) Å
c = 7.8642 (6) Å
β = 114.043 (1)°
V = 928.47 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 (2) K
0.75 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▶) T _min = 0.924, T _max = 0.993
15216 measured reflections
2209 independent reflections
1951 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.098
S = 1.02
2209 reflections
167 parameters
All H-atom parameters refined
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶), PLATON (Spek, 2003 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005436/ci2565sup1.cif

e-64-0o653-sup1.cif^{(15.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005436/ci2565Isup2.hkl

e-64-0o653-Isup2.hkl^{(106.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯N1	0.94 (2)	2.438 (14)	2.8596 (14)	107 (1)
C1—H1⋯O2ⁱ	0.96 (2)	2.588 (15)	3.4581 (14)	150 (1)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Oximes and their derivatives such as O-ethers and esters are important intermediates in organic chemistry and are well known in both analytical and coordination chemistry (Robertson, 1995). These compounds are also of interest as biologically active compounds (Van Helden et al., 1996). In this in mind we have decided to synthesize and structurally characterize a set of O-acryloyl oximes of 6-membered aza-heterocycles as 1,2,4-triazine, pyridine and pyrazine. These compounds were obtained by reaction of appropriate oximes and 3-bromopropanoyl chloride under Staudinger reaction conditions. As a part of our ongoing studies, we report herein the crystal and molecular structure of the title compound.

The geometric parameters (bond lengths, angles and torsion angles) in the title compound are very similar to those observed in a previously reported structure of (E)-1-(3-methylsulfanyl-1,2,4-triazin-5-yl)-ethanone O-acryloyl oxime (Mojzych et al., 2007). The oxime group is in trans and the acryloyl group in s-cis conformation with the torsion angles O1—N2—C6—C5 and O2—C7—C8—C9 of 179.39 (7) and 2.73 (16)°, respectively. The molecule as a whole adopts a nearly planar chain-extended conformation (Fig. 1). This conformation is stabilized by an intramolecular C10—H10B···N1 hydrogen bond leading to the formation of a five-membered ring described by the S(5) graph-set symbol (Bernstein et al., 1995).

In the crystal structure, the screw-related molecules are linked to form C(9) chains along the [010] direction by C1—H1···O2 intermolecular hydrogen bonds (Fig. 2).

Experimental

To a solution of 2-acetylpyridine (204 mg, 1.5 mmol) and triethylamine (454 mg, 4.5 mmol) in dry CH₂Cl₂ (5 ml) at 233 K was added 3-bromopropionyl chloride (1.5 mmol) in CH₂Cl₂ (2 ml) dropwise. The reaction mixture was allowed to warm to room temperature and was stirred for 12 h. It was then washed with water (2 × 10 ml), saturated aqueous sodium bicarbonate (3 × 10 ml), brine (1 × 10 ml) and dried over MgSO₄. Removal of the solvent yielded the crude product which was then purified by column chromatography on silica gel using CH₂Cl₂-hexane mixture (2:1) as eluent to afford the title compound as a colourless solid. Yield: 216 mg (76%) and m.p. 338 K. Single crystals suitable for X-ray diffraction analysis were grown by slow evaporation of an ethanol solution. ¹H NMR (CDCl₃) δ: 2.55 (s, 3H), 5.99–6.02 (d, 1H, J = 10.5 Hz), 6.29–6.38 (dd, 1H, J = 10.5 Hz), 6.59–6.65 (d, 1H, J = 17.4 Hz), 7.34–7.38 (t, 1H, J = 6.6 Hz), 7.72–7.78 (t, 1H, J = 8.1 Hz), 8.12 - 8.15 (d, 1H, J = 8.1 Hz), 8.65–8.67 (d, 1H, J = 6.6 Hz). ¹³C NMR (CDCl₃) δ: 13.11, 122.28, 125.27, 126.72, 132.59, 136.78, 149.34, 152.89, 163.71, 164.28. HR—MS (m/z) for C₁₀H₁₁N₂O₂: 191.0822 [M⁺+H]; calcd. 191.0821.