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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o653.
Published online 2008 March 5. doi:  10.1107/S1600536808005436
PMCID: PMC2961001

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

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 [triangle]). For the biological activity of oximes, see: Van Helden et al. (1996 [triangle]). For related structures, see: Mojzych et al. (2007 [triangle]). For the graph-set notation, see: Bernstein et al. (1995 [triangle]).

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Object name is e-64-0o653-scheme1.jpg

Experimental

Crystal data

  • C10H10N2O2
  • M r = 190.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o653-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.18 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

All H atoms were located in a difference Fourier map and were refined isotropically [C—H = 0.929 (15)–0.989 (15) Å].

Figures

Fig. 1.
The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
A view of the molecular packing in the title compound. Dashed lines indicate intermolecular hydrogen bonds.

Crystal data

C10H10N2O2F000 = 400
Mr = 190.20Dx = 1.361 Mg m3
Monoclinic, P21/nMelting point: 338 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71073 Å
a = 7.0240 (5) ÅCell parameters from 166 reflections
b = 18.4054 (14) Åθ = 3.8–28.0º
c = 7.8642 (6) ŵ = 0.10 mm1
β = 114.043 (1)ºT = 100 (2) K
V = 928.47 (12) Å3Prism, colourless
Z = 40.75 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer1951 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
T = 100(2) Kθmax = 28.4º
ω scansθmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 2002)h = −9→9
Tmin = 0.924, Tmax = 0.993k = −24→24
15216 measured reflectionsl = −10→10
2209 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033All H-atom parameters refined
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0531P)2 + 0.3208P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2209 reflectionsΔρmax = 0.40 e Å3
167 parametersΔρmin = −0.18 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.29133 (11)−0.01660 (4)0.63817 (9)0.01600 (18)
O20.12879 (12)−0.12207 (4)0.50393 (10)0.02091 (19)
N10.27586 (13)0.17974 (5)0.26737 (12)0.0168 (2)
N20.23265 (12)0.01032 (5)0.45236 (11)0.0149 (2)
C10.22032 (15)0.21070 (6)0.09936 (15)0.0189 (2)
C20.14439 (15)0.17215 (6)−0.06672 (15)0.0189 (2)
C30.13150 (15)0.09699 (6)−0.06045 (14)0.0176 (2)
C40.19186 (15)0.06379 (6)0.11195 (14)0.0157 (2)
C50.25793 (14)0.10712 (5)0.27155 (14)0.0139 (2)
C60.30844 (14)0.07431 (5)0.45895 (13)0.0137 (2)
C70.22368 (15)−0.08629 (5)0.63995 (14)0.0148 (2)
C80.28945 (16)−0.10972 (6)0.83633 (15)0.0184 (2)
C90.25144 (17)−0.17670 (6)0.87484 (16)0.0212 (2)
C100.43601 (17)0.11625 (6)0.63073 (14)0.0179 (2)
H10.234 (2)0.2626 (8)0.0980 (19)0.023 (3)*
H20.106 (2)0.1958 (8)−0.180 (2)0.026 (3)*
H30.081 (2)0.0693 (8)−0.173 (2)0.027 (3)*
H40.185 (2)0.0111 (7)0.1226 (18)0.021 (3)*
H80.363 (2)−0.0726 (8)0.931 (2)0.030 (4)*
H9A0.293 (2)−0.1938 (7)1.002 (2)0.025 (3)*
H9B0.180 (2)−0.2100 (7)0.776 (2)0.025 (3)*
H10A0.389 (2)0.1079 (8)0.726 (2)0.038 (4)*
H10B0.429 (2)0.1661 (9)0.605 (2)0.039 (4)*
H10C0.581 (3)0.1023 (8)0.673 (2)0.039 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0177 (4)0.0178 (4)0.0120 (3)−0.0008 (3)0.0056 (3)0.0015 (3)
O20.0281 (4)0.0172 (4)0.0168 (4)−0.0010 (3)0.0085 (3)−0.0012 (3)
N10.0150 (4)0.0154 (4)0.0200 (4)0.0006 (3)0.0072 (3)0.0004 (3)
N20.0158 (4)0.0173 (4)0.0119 (4)0.0022 (3)0.0059 (3)0.0022 (3)
C10.0168 (5)0.0153 (5)0.0244 (5)0.0010 (4)0.0081 (4)0.0033 (4)
C20.0154 (5)0.0227 (5)0.0181 (5)0.0023 (4)0.0064 (4)0.0067 (4)
C30.0152 (5)0.0220 (5)0.0154 (5)−0.0014 (4)0.0060 (4)−0.0011 (4)
C40.0147 (4)0.0154 (5)0.0176 (5)0.0000 (3)0.0072 (4)0.0004 (4)
C50.0104 (4)0.0162 (5)0.0155 (5)0.0013 (3)0.0058 (3)0.0005 (4)
C60.0115 (4)0.0160 (5)0.0149 (5)0.0024 (3)0.0067 (3)−0.0007 (4)
C70.0131 (4)0.0163 (5)0.0169 (5)0.0031 (3)0.0080 (4)0.0013 (4)
C80.0167 (5)0.0237 (5)0.0156 (5)0.0008 (4)0.0073 (4)0.0013 (4)
C90.0212 (5)0.0241 (6)0.0208 (5)0.0039 (4)0.0110 (4)0.0051 (4)
C100.0205 (5)0.0181 (5)0.0154 (5)−0.0027 (4)0.0077 (4)−0.0025 (4)

Geometric parameters (Å, °)

O1—C71.3698 (12)C4—C51.3971 (14)
O1—N21.4352 (10)C4—H40.976 (13)
O2—C71.2005 (13)C5—C61.4954 (13)
N1—C11.3426 (14)C6—C101.4957 (13)
N1—C51.3442 (13)C7—C81.4843 (14)
N2—C61.2849 (13)C8—C91.3224 (15)
C1—C21.3879 (15)C8—H80.989 (15)
C1—H10.962 (14)C9—H9A0.972 (15)
C2—C31.3884 (15)C9—H9B0.954 (14)
C2—H20.929 (15)C10—H10A0.947 (17)
C3—C41.3868 (14)C10—H10B0.937 (16)
C3—H30.954 (15)C10—H10C0.969 (16)
C7—O1—N2112.13 (7)N2—C6—C5113.73 (8)
C1—N1—C5116.97 (9)N2—C6—C10126.54 (9)
C6—N2—O1109.45 (8)C5—C6—C10119.74 (8)
N1—C1—C2123.73 (10)O2—C7—O1125.00 (9)
N1—C1—H1116.3 (8)O2—C7—C8126.30 (9)
C2—C1—H1120.0 (8)O1—C7—C8108.69 (8)
C3—C2—C1118.79 (9)C9—C8—C7120.19 (10)
C3—C2—H2120.2 (9)C9—C8—H8124.2 (9)
C1—C2—H2121.0 (9)C7—C8—H8115.5 (9)
C4—C3—C2118.38 (9)C8—C9—H9A122.2 (8)
C4—C3—H3121.3 (8)C8—C9—H9B120.1 (8)
C2—C3—H3120.3 (8)H9A—C9—H9B117.7 (11)
C3—C4—C5118.96 (9)C6—C10—H10A111.0 (10)
C3—C4—H4121.0 (8)C6—C10—H10B110.3 (10)
C5—C4—H4120.0 (8)H10A—C10—H10B109.1 (13)
N1—C5—C4123.07 (9)C6—C10—H10C109.4 (9)
N1—C5—C6116.01 (8)H10A—C10—H10C109.9 (13)
C4—C5—C6120.90 (9)H10B—C10—H10C107.0 (13)
C7—O1—N2—C6−176.92 (7)O1—N2—C6—C10−0.77 (13)
C5—N1—C1—C20.84 (14)N1—C5—C6—N2160.49 (8)
N1—C1—C2—C3−2.47 (15)C4—C5—C6—N2−18.13 (12)
C1—C2—C3—C41.12 (14)N1—C5—C6—C10−19.37 (12)
C2—C3—C4—C51.61 (14)C4—C5—C6—C10162.02 (9)
C1—N1—C5—C42.13 (14)N2—O1—C7—O20.98 (13)
C1—N1—C5—C6−176.46 (8)N2—O1—C7—C8−179.69 (7)
C3—C4—C5—N1−3.38 (14)O2—C7—C8—C92.73 (16)
C3—C4—C5—C6175.14 (8)O1—C7—C8—C9−176.58 (9)
O1—N2—C6—C5179.39 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C10—H10B···N10.94 (2)2.438 (14)2.8596 (14)107 (1)
C1—H1···O2i0.96 (2)2.588 (15)3.4581 (14)150 (1)

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2565).

References

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  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Mojzych, M., Karczmarzyk, Z., Fruziński, A. & Rykowski, A. (2007). Anal. Sci. (X-Ray Str. Anal. Online), 23, x205–x206.
  • Robertson, G. M. (1995). Comprehensive Organic Functional Group Transformation, Vol. 3, edited by A. R. Katritzky, O. Meth-Cohn & C. W. Rees, pp. 425–441. Oxford: Elsevier.
  • Sheldrick, G. M. (2002). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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  • Van Helden, F. P. M., Busker, R. W., Melchers, B. P. C. & Bruijnzeel, P. L. B. (1996). Arch. Toxicol.70, 779–786. [PubMed]

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