Acta Cryst. (2008). E64, o653 [ doi:10.1107/S1600536808005436 ]
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-HO hydrogen bonds.
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.
All H atoms were located in a difference Fourier map and were refined isotropically [C—H = 0.929 (15)–0.989 (15) Å].
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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).
![[Figure 1]](./ci2565fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./ci2565fig2thm.gif)
| Fig. 2. A view of the molecular packing in the title compound. Dashed lines indicate intermolecular hydrogen bonds. |
| C10H10N2O2 | F000 = 400 |
| Mr = 190.20 | Dx = 1.361 Mg m−3 |
| Monoclinic, P21/n | Melting point: 338 K |
| Hall symbol: -P 2yn | Mo Kα radiation λ = 0.71073 Å |
| a = 7.0240 (5) Å | Cell parameters from 166 reflections |
| b = 18.4054 (14) Å | θ = 3.8–28.0º |
| c = 7.8642 (6) Å | µ = 0.10 mm−1 |
| β = 114.043 (1)º | T = 100 (2) K |
| V = 928.47 (12) Å3 | Prism, colourless |
| Z = 4 | 0.75 × 0.13 × 0.07 mm |
| Bruker SMART APEXII CCD diffractometer | 1951 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.035 |
| T = 100(2) K | θmax = 28.4º |
| ω scans | θmin = 2.2º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −9→9 |
| Tmin = 0.924, Tmax = 0.993 | k = −24→24 |
| 15216 measured reflections | l = −10→10 |
| 2209 independent reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.033 | All 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 reflections | Δρmax = 0.40 e Å−3 |
| 167 parameters | Δρmin = −0.18 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C10H10N2O2 | V = 928.47 (12) Å3 |
| Mr = 190.20 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 7.0240 (5) Å | µ = 0.10 mm−1 |
| b = 18.4054 (14) Å | T = 100 (2) K |
| c = 7.8642 (6) Å | 0.75 × 0.13 × 0.07 mm |
| β = 114.043 (1)º |
| Bruker SMART APEXII CCD diffractometer | 2209 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1951 reflections with I > 2σ(I) |
| Tmin = 0.924, Tmax = 0.993 | Rint = 0.035 |
| 15216 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 167 parameters |
| wR(F2) = 0.098 | All H-atom parameters refined |
| S = 1.03 | Δρmax = 0.40 e Å−3 |
| 2209 reflections | Δρmin = −0.18 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.29133 (11) | −0.01660 (4) | 0.63817 (9) | 0.01600 (18) | |
| O2 | 0.12879 (12) | −0.12207 (4) | 0.50393 (10) | 0.02091 (19) | |
| N1 | 0.27586 (13) | 0.17974 (5) | 0.26737 (12) | 0.0168 (2) | |
| N2 | 0.23265 (12) | 0.01032 (5) | 0.45236 (11) | 0.0149 (2) | |
| C1 | 0.22032 (15) | 0.21070 (6) | 0.09936 (15) | 0.0189 (2) | |
| C2 | 0.14439 (15) | 0.17215 (6) | −0.06672 (15) | 0.0189 (2) | |
| C3 | 0.13150 (15) | 0.09699 (6) | −0.06045 (14) | 0.0176 (2) | |
| C4 | 0.19186 (15) | 0.06379 (6) | 0.11195 (14) | 0.0157 (2) | |
| C5 | 0.25793 (14) | 0.10712 (5) | 0.27155 (14) | 0.0139 (2) | |
| C6 | 0.30844 (14) | 0.07431 (5) | 0.45895 (13) | 0.0137 (2) | |
| C7 | 0.22368 (15) | −0.08629 (5) | 0.63995 (14) | 0.0148 (2) | |
| C8 | 0.28945 (16) | −0.10972 (6) | 0.83633 (15) | 0.0184 (2) | |
| C9 | 0.25144 (17) | −0.17670 (6) | 0.87484 (16) | 0.0212 (2) | |
| C10 | 0.43601 (17) | 0.11625 (6) | 0.63073 (14) | 0.0179 (2) | |
| H1 | 0.234 (2) | 0.2626 (8) | 0.0980 (19) | 0.023 (3)* | |
| H2 | 0.106 (2) | 0.1958 (8) | −0.180 (2) | 0.026 (3)* | |
| H3 | 0.081 (2) | 0.0693 (8) | −0.173 (2) | 0.027 (3)* | |
| H4 | 0.185 (2) | 0.0111 (7) | 0.1226 (18) | 0.021 (3)* | |
| H8 | 0.363 (2) | −0.0726 (8) | 0.931 (2) | 0.030 (4)* | |
| H9A | 0.293 (2) | −0.1938 (7) | 1.002 (2) | 0.025 (3)* | |
| H9B | 0.180 (2) | −0.2100 (7) | 0.776 (2) | 0.025 (3)* | |
| H10A | 0.389 (2) | 0.1079 (8) | 0.726 (2) | 0.038 (4)* | |
| H10B | 0.429 (2) | 0.1661 (9) | 0.605 (2) | 0.039 (4)* | |
| H10C | 0.581 (3) | 0.1023 (8) | 0.673 (2) | 0.039 (4)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0177 (4) | 0.0178 (4) | 0.0120 (3) | −0.0008 (3) | 0.0056 (3) | 0.0015 (3) |
| O2 | 0.0281 (4) | 0.0172 (4) | 0.0168 (4) | −0.0010 (3) | 0.0085 (3) | −0.0012 (3) |
| N1 | 0.0150 (4) | 0.0154 (4) | 0.0200 (4) | 0.0006 (3) | 0.0072 (3) | 0.0004 (3) |
| N2 | 0.0158 (4) | 0.0173 (4) | 0.0119 (4) | 0.0022 (3) | 0.0059 (3) | 0.0022 (3) |
| C1 | 0.0168 (5) | 0.0153 (5) | 0.0244 (5) | 0.0010 (4) | 0.0081 (4) | 0.0033 (4) |
| C2 | 0.0154 (5) | 0.0227 (5) | 0.0181 (5) | 0.0023 (4) | 0.0064 (4) | 0.0067 (4) |
| C3 | 0.0152 (5) | 0.0220 (5) | 0.0154 (5) | −0.0014 (4) | 0.0060 (4) | −0.0011 (4) |
| C4 | 0.0147 (4) | 0.0154 (5) | 0.0176 (5) | 0.0000 (3) | 0.0072 (4) | 0.0004 (4) |
| C5 | 0.0104 (4) | 0.0162 (5) | 0.0155 (5) | 0.0013 (3) | 0.0058 (3) | 0.0005 (4) |
| C6 | 0.0115 (4) | 0.0160 (5) | 0.0149 (5) | 0.0024 (3) | 0.0067 (3) | −0.0007 (4) |
| C7 | 0.0131 (4) | 0.0163 (5) | 0.0169 (5) | 0.0031 (3) | 0.0080 (4) | 0.0013 (4) |
| C8 | 0.0167 (5) | 0.0237 (5) | 0.0156 (5) | 0.0008 (4) | 0.0073 (4) | 0.0013 (4) |
| C9 | 0.0212 (5) | 0.0241 (6) | 0.0208 (5) | 0.0039 (4) | 0.0110 (4) | 0.0051 (4) |
| C10 | 0.0205 (5) | 0.0181 (5) | 0.0154 (5) | −0.0027 (4) | 0.0077 (4) | −0.0025 (4) |
| O1—C7 | 1.3698 (12) | C4—C5 | 1.3971 (14) |
| O1—N2 | 1.4352 (10) | C4—H4 | 0.976 (13) |
| O2—C7 | 1.2005 (13) | C5—C6 | 1.4954 (13) |
| N1—C1 | 1.3426 (14) | C6—C10 | 1.4957 (13) |
| N1—C5 | 1.3442 (13) | C7—C8 | 1.4843 (14) |
| N2—C6 | 1.2849 (13) | C8—C9 | 1.3224 (15) |
| C1—C2 | 1.3879 (15) | C8—H8 | 0.989 (15) |
| C1—H1 | 0.962 (14) | C9—H9A | 0.972 (15) |
| C2—C3 | 1.3884 (15) | C9—H9B | 0.954 (14) |
| C2—H2 | 0.929 (15) | C10—H10A | 0.947 (17) |
| C3—C4 | 1.3868 (14) | C10—H10B | 0.937 (16) |
| C3—H3 | 0.954 (15) | C10—H10C | 0.969 (16) |
| C7—O1—N2 | 112.13 (7) | N2—C6—C5 | 113.73 (8) |
| C1—N1—C5 | 116.97 (9) | N2—C6—C10 | 126.54 (9) |
| C6—N2—O1 | 109.45 (8) | C5—C6—C10 | 119.74 (8) |
| N1—C1—C2 | 123.73 (10) | O2—C7—O1 | 125.00 (9) |
| N1—C1—H1 | 116.3 (8) | O2—C7—C8 | 126.30 (9) |
| C2—C1—H1 | 120.0 (8) | O1—C7—C8 | 108.69 (8) |
| C3—C2—C1 | 118.79 (9) | C9—C8—C7 | 120.19 (10) |
| C3—C2—H2 | 120.2 (9) | C9—C8—H8 | 124.2 (9) |
| C1—C2—H2 | 121.0 (9) | C7—C8—H8 | 115.5 (9) |
| C4—C3—C2 | 118.38 (9) | C8—C9—H9A | 122.2 (8) |
| C4—C3—H3 | 121.3 (8) | C8—C9—H9B | 120.1 (8) |
| C2—C3—H3 | 120.3 (8) | H9A—C9—H9B | 117.7 (11) |
| C3—C4—C5 | 118.96 (9) | C6—C10—H10A | 111.0 (10) |
| C3—C4—H4 | 121.0 (8) | C6—C10—H10B | 110.3 (10) |
| C5—C4—H4 | 120.0 (8) | H10A—C10—H10B | 109.1 (13) |
| N1—C5—C4 | 123.07 (9) | C6—C10—H10C | 109.4 (9) |
| N1—C5—C6 | 116.01 (8) | H10A—C10—H10C | 109.9 (13) |
| C4—C5—C6 | 120.90 (9) | H10B—C10—H10C | 107.0 (13) |
| C7—O1—N2—C6 | −176.92 (7) | O1—N2—C6—C10 | −0.77 (13) |
| C5—N1—C1—C2 | 0.84 (14) | N1—C5—C6—N2 | 160.49 (8) |
| N1—C1—C2—C3 | −2.47 (15) | C4—C5—C6—N2 | −18.13 (12) |
| C1—C2—C3—C4 | 1.12 (14) | N1—C5—C6—C10 | −19.37 (12) |
| C2—C3—C4—C5 | 1.61 (14) | C4—C5—C6—C10 | 162.02 (9) |
| C1—N1—C5—C4 | 2.13 (14) | N2—O1—C7—O2 | 0.98 (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—C9 | 2.73 (16) |
| C3—C4—C5—C6 | 175.14 (8) | O1—C7—C8—C9 | −176.58 (9) |
| O1—N2—C6—C5 | 179.39 (7) |
| 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) |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2. |
| 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) |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2. |
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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).