Acta Cryst. (2008). E64, o1983 [ doi:10.1107/S1600536808029838 ]
In the title compound, C13H14Cl2O, the carbonyl and ethenyl groups are coplanar with the aromatic ring. There are four molecules in the asymmetric unit and all atoms in the molecule lie on mirror planes. The molecules are packed in an offset face-to-face arrangement showing ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking interactions involving the benzene rings [centroid-centroid distance = 3.564 (2) Å].
3,3-dimethylbutan-2-one(0.0105 mol) was added dropwise into a solution of 2,4-dichlorobenzaldehyde (0.01 mol) and 60 ml ethanol. Then 0.1 g 50% NaOH solution as catalyst was added and the reaction was stirred at 333 K for 5 h . The solvent was evaporated to about half volume, then cooled to 277 K and the precipitate formed.This was filtered and dried to give the desired product (yield: 94.7%). Crystals suitable for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.
The methyl H atoms were positioned geometrically (C—H=0.98 Å) and torsion angles refined to fit the electron density [Uiso(H) = 1.5Ueq(C)]. Other H atoms were placed in calculated position (methylene C—H = 0.95Å and aromatic C—H=0.95 Å) and refined as riding [Uiso(H) = 1.2Ueq(C)].
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./sg2260fig1thm.gif)
| Fig. 1. Molecular structure showing 30% probability displacement ellipsoids.H atoms are omitted for clarity. |
![[Figure 2]](./sg2260fig2thm.gif)
| Fig. 2. Packing diagram showing π–π stacking interactions. |
| C13H14Cl2O | Dx = 1.390 Mg m−3 |
| Mr = 257.14 | Melting point: 385 K |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 3552 reflections |
| a = 11.2553 (7) Å | θ = 2.2–27.0° |
| b = 7.0458 (4) Å | µ = 0.50 mm−1 |
| c = 15.4969 (9) Å | T = 173 K |
| V = 1228.94 (13) Å3 | Block, colorless |
| Z = 4 | 0.47 × 0.39 × 0.15 mm |
| F(000) = 536 |
| Bruker SMART 1000 CCD diffractometer | 1444 independent reflections |
| Radiation source: fine-focus sealed tube | 1227 reflections with I > 2σ(I) |
| graphite | Rint = 0.021 |
| ω scans | θmax = 27.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −12→14 |
| Tmin = 0.798, Tmax = 0.928 | k = −8→9 |
| 6162 measured reflections | l = −19→14 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.085 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0391P)2 + 0.6612P] where P = (Fo2 + 2Fc2)/3 |
| 1444 reflections | (Δ/σ)max < 0.001 |
| 95 parameters | Δρmax = 0.28 e Å−3 |
| 0 restraints | Δρmin = −0.36 e Å−3 |
| C13H14Cl2O | V = 1228.94 (13) Å3 |
| Mr = 257.14 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 11.2553 (7) Å | µ = 0.50 mm−1 |
| b = 7.0458 (4) Å | T = 173 K |
| c = 15.4969 (9) Å | 0.47 × 0.39 × 0.15 mm |
| Bruker SMART 1000 CCD diffractometer | 1444 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1227 reflections with I > 2σ(I) |
| Tmin = 0.798, Tmax = 0.928 | Rint = 0.021 |
| 6162 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
| wR(F2) = 0.085 | Δρmax = 0.28 e Å−3 |
| S = 1.07 | Δρmin = −0.36 e Å−3 |
| 1444 reflections | Absolute structure: ? |
| 95 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Occ. (<1) | |
| Cl1 | 0.73794 (5) | 0.2500 | 0.45333 (4) | 0.03276 (17) | |
| Cl2 | 0.34147 (5) | 0.2500 | 0.26347 (3) | 0.03138 (17) | |
| C1 | 0.57275 (19) | 0.2500 | 0.61286 (13) | 0.0239 (4) | |
| H1 | 0.6571 | 0.2500 | 0.6149 | 0.029* | |
| C2 | 0.51505 (19) | 0.2500 | 0.68766 (13) | 0.0265 (5) | |
| H2 | 0.4307 | 0.2500 | 0.6869 | 0.032* | |
| C3 | 0.57686 (18) | 0.2500 | 0.77240 (13) | 0.0225 (4) | |
| C4 | 0.49783 (18) | 0.2500 | 0.85260 (12) | 0.0227 (4) | |
| C5 | 0.5740 (2) | 0.2500 | 0.93380 (14) | 0.0314 (5) | |
| H5A | 0.6163 | 0.1518 | 0.9347 | 0.047* | 0.50 |
| H5B | 0.5225 | 0.2500 | 0.9848 | 0.047* | |
| H5C | 0.6252 | 0.3625 | 0.9340 | 0.047* | 0.50 |
| C6 | 0.41949 (13) | 0.0709 (2) | 0.85096 (10) | 0.0285 (3) | |
| H6A | 0.3670 | 0.0751 | 0.8005 | 0.043* | |
| H6B | 0.3714 | 0.0656 | 0.9036 | 0.043* | |
| H6C | 0.4701 | −0.0421 | 0.8477 | 0.043* | |
| C7 | 0.51674 (18) | 0.2500 | 0.52726 (13) | 0.0224 (4) | |
| C8 | 0.58317 (17) | 0.2500 | 0.45064 (13) | 0.0217 (4) | |
| C9 | 0.53111 (19) | 0.2500 | 0.36945 (13) | 0.0244 (4) | |
| H9 | 0.5785 | 0.2500 | 0.3187 | 0.029* | |
| C10 | 0.40892 (19) | 0.2500 | 0.36426 (13) | 0.0241 (4) | |
| C11 | 0.33861 (18) | 0.2500 | 0.43745 (15) | 0.0267 (5) | |
| H11 | 0.2544 | 0.2500 | 0.4329 | 0.032* | |
| C12 | 0.39335 (19) | 0.2500 | 0.51767 (14) | 0.0265 (5) | |
| H12 | 0.3451 | 0.2500 | 0.5680 | 0.032* | |
| O1 | 0.68512 (13) | 0.2500 | 0.77742 (10) | 0.0323 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0204 (3) | 0.0528 (4) | 0.0251 (3) | 0.000 | 0.00297 (19) | 0.000 |
| Cl2 | 0.0291 (3) | 0.0413 (3) | 0.0237 (3) | 0.000 | −0.0039 (2) | 0.000 |
| C1 | 0.0243 (10) | 0.0245 (10) | 0.0228 (10) | 0.000 | 0.0018 (8) | 0.000 |
| C2 | 0.0232 (10) | 0.0337 (12) | 0.0225 (10) | 0.000 | −0.0004 (8) | 0.000 |
| C3 | 0.0221 (10) | 0.0236 (10) | 0.0218 (10) | 0.000 | 0.0009 (8) | 0.000 |
| C4 | 0.0202 (9) | 0.0284 (11) | 0.0195 (9) | 0.000 | 0.0007 (8) | 0.000 |
| C5 | 0.0256 (11) | 0.0463 (14) | 0.0223 (10) | 0.000 | −0.0029 (9) | 0.000 |
| C6 | 0.0269 (7) | 0.0303 (8) | 0.0285 (8) | −0.0032 (6) | 0.0043 (6) | 0.0008 (6) |
| C7 | 0.0238 (10) | 0.0204 (10) | 0.0229 (10) | 0.000 | 0.0011 (8) | 0.000 |
| C8 | 0.0190 (9) | 0.0209 (10) | 0.0252 (10) | 0.000 | 0.0019 (8) | 0.000 |
| C9 | 0.0276 (11) | 0.0240 (10) | 0.0217 (10) | 0.000 | 0.0039 (8) | 0.000 |
| C10 | 0.0286 (11) | 0.0220 (10) | 0.0217 (10) | 0.000 | −0.0019 (8) | 0.000 |
| C11 | 0.0205 (10) | 0.0311 (12) | 0.0285 (11) | 0.000 | 0.0005 (8) | 0.000 |
| C12 | 0.0256 (11) | 0.0310 (11) | 0.0228 (10) | 0.000 | 0.0055 (8) | 0.000 |
| O1 | 0.0200 (7) | 0.0468 (10) | 0.0301 (8) | 0.000 | 0.0026 (6) | 0.000 |
| Cl1—C8 | 1.742 (2) | C5—H5C | 0.9800 |
| Cl2—C10 | 1.737 (2) | C6—H6A | 0.9800 |
| C1—C2 | 1.329 (3) | C6—H6B | 0.9800 |
| C1—C7 | 1.469 (3) | C6—H6C | 0.9800 |
| C1—H1 | 0.9500 | C7—C12 | 1.397 (3) |
| C2—C3 | 1.486 (3) | C7—C8 | 1.403 (3) |
| C2—H2 | 0.9500 | C8—C9 | 1.388 (3) |
| C3—O1 | 1.221 (2) | C9—C10 | 1.378 (3) |
| C3—C4 | 1.528 (3) | C9—H9 | 0.9500 |
| C4—C5 | 1.522 (3) | C10—C11 | 1.383 (3) |
| C4—C6 | 1.5398 (19) | C11—C12 | 1.387 (3) |
| C4—C6i | 1.5398 (19) | C11—H11 | 0.9500 |
| C5—H5A | 0.8400 | C12—H12 | 0.9500 |
| C5—H5B | 0.9799 | ||
| C2—C1—C7 | 125.3 (2) | H6A—C6—H6B | 109.5 |
| C2—C1—H1 | 117.3 | C4—C6—H6C | 109.5 |
| C7—C1—H1 | 117.3 | H6A—C6—H6C | 109.5 |
| C1—C2—C3 | 122.83 (19) | H6B—C6—H6C | 109.5 |
| C1—C2—H2 | 118.6 | C12—C7—C8 | 116.09 (18) |
| C3—C2—H2 | 118.6 | C12—C7—C1 | 121.53 (19) |
| O1—C3—C2 | 121.57 (19) | C8—C7—C1 | 122.39 (18) |
| O1—C3—C4 | 121.93 (18) | C9—C8—C7 | 122.84 (19) |
| C2—C3—C4 | 116.50 (17) | C9—C8—Cl1 | 116.34 (15) |
| C5—C4—C3 | 110.15 (17) | C7—C8—Cl1 | 120.82 (15) |
| C5—C4—C6 | 109.64 (11) | C10—C9—C8 | 118.32 (19) |
| C3—C4—C6 | 108.65 (11) | C10—C9—H9 | 120.8 |
| C5—C4—C6i | 109.64 (11) | C8—C9—H9 | 120.8 |
| C3—C4—C6i | 108.65 (11) | C9—C10—C11 | 121.55 (19) |
| C6—C4—C6i | 110.09 (17) | C9—C10—Cl2 | 119.27 (16) |
| C4—C5—H5A | 109.5 | C11—C10—Cl2 | 119.17 (16) |
| C4—C5—H5B | 109.5 | C10—C11—C12 | 118.73 (19) |
| H5A—C5—H5B | 108.7 | C10—C11—H11 | 120.6 |
| C4—C5—H5C | 109.4 | C12—C11—H11 | 120.6 |
| H5A—C5—H5C | 109.5 | C11—C12—C7 | 122.5 (2) |
| H5B—C5—H5C | 110.2 | C11—C12—H12 | 118.8 |
| C4—C6—H6A | 109.5 | C7—C12—H12 | 118.8 |
| C4—C6—H6B | 109.5 | ||
| C7—C1—C2—C3 | 180.0 | C1—C7—C8—C9 | 180.0 |
| C1—C2—C3—O1 | 0.0 | C12—C7—C8—Cl1 | 180.0 |
| C1—C2—C3—C4 | 180.0 | C1—C7—C8—Cl1 | 0.0 |
| O1—C3—C4—C5 | 0.0 | C7—C8—C9—C10 | 0.0 |
| C2—C3—C4—C5 | 180.0 | Cl1—C8—C9—C10 | 180.0 |
| O1—C3—C4—C6 | −120.11 (11) | C8—C9—C10—C11 | 0.0 |
| C2—C3—C4—C6 | 59.89 (11) | C8—C9—C10—Cl2 | 180.0 |
| O1—C3—C4—C6i | 120.11 (11) | C9—C10—C11—C12 | 0.0 |
| C2—C3—C4—C6i | −59.89 (11) | Cl2—C10—C11—C12 | 180.0 |
| C2—C1—C7—C12 | 0.0 | C10—C11—C12—C7 | 0.0 |
| C2—C1—C7—C8 | 180.0 | C8—C7—C12—C11 | 0.0 |
| C12—C7—C8—C9 | 0.0 | C1—C7—C12—C11 | 180.0 |
| Symmetry codes: (i) x, −y+1/2, z. |
The authors express their thanks to the State Key Laboratory of Chemo/Biosensing and Chemometrics (Hunan University) (200414) and [is something missing here?]
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wang, Y., Hu, A.-X., Chen, P., Chen, M. & Liu, Zh.-L. (2006). Chin. Agrochem. 45, 397–398.
Phenyl-4,4-dimethylpentan-3-one derivatives are important intermediates in medicinal industry (Wang et al., 2006). Herein we report the synthesis and crystal structure of 1-(2,4-dichlorophen-yl)-4,4-dimethylpentan-3-one.