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access8-Chloro-2-methylquinoline
aCollege of Chemistry and Chemical Engineering, Hunan University, 410082 Changsha, People's Republic of China
*Correspondence e-mail: axhu0731@yahoo.com.cn
In the title compound, C10H8ClN, the crystal packing shows π–π stacking between the heterocyclic ring and the aromatic ring, with a centroid–centroid distance of 3.819 Å. The crystal studied was a racemic twin, the ratio of the twin components being 0.65 (7):0.35 (7).
Related literature
The title compound is an important intermediate in the pharmaceutical industry, see: Shen & Hartwig (2006![[Shen, Q.-L. & Hartwig, F. (2006). J. Am. Chem. Soc. 128, 10028-10029.]](../../../../../../logos/arrows/e_arr.gif "Shen, Q.-L. & Hartwig, F. (2006). J. Am. Chem. Soc. 128, 10028-10029.")
); Ranu et al. (2000); Lee & Hartwig (2005).
![[Scheme 1]](bt2969scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2001); cell SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536809020194/bt2969sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809020194/bt2969Isup2.hkl
A solution of 13 g of 2-chloroaniline in 200 mL chlorobenzene and 0.5 g of p-toluenesulfonic acid was heated to 393 K. 14 g of crotonaldehyde were added dropwise with in 1 h, then refluxed for 2 h. The solution was concentrated under reduced pressure to give rude product, which was then recrystallizated from dimethylbenzene to get 10 g of the product as a white solid. The yield was 57%. Crystals suitable for X-ray were obtained by slow evaporation of an ethanol solution at room temperature.
H atom were positioned geometrically (Caromatic—H = 0.95 Å, Cmethyl—H = 0.98 Å) and refined as riding with Uiso(H) = 1.2Ueq(Caromatic) or Uiso(H) = 1.5Ueq(Cmethyl). The crystal under investigation turned out to be a racemic twin with a ratio of the twin components of 0.65 (7) to 0.35 (7).
Data collection: SMART (Bruker, 2001); cell SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./bt2969fig1thm.gif) | Fig. 1. Molecular structure of the title compound showing 50% probability displacement ellipsoids. |
| C10H8ClN | Dx = 1.387 Mg m−3 |
| Mr = 177.62 | Melting point: 333 K |
| Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2c -2ac | Cell parameters from 2761 reflections |
| a = 12.7961 (9) Å | θ = 3.1–27.0° |
| b = 5.0660 (4) Å | µ = 0.39 mm−1 |
| c = 13.1181 (9) Å | T = 173 K |
| V = 850.38 (11) Å3 | Block, colourless |
| Z = 4 | 0.47 × 0.46 × 0.23 mm |
| F(000) = 368 |
| Bruker SMART 1000 CCD diffractometer | 1821 independent reflections |
| Radiation source: fine-focus sealed tube | 1703 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.016 |
| ω scans | θmax = 27.1°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −16→16 |
| Tmin = 0.840, Tmax = 0.917 | k = −2→6 |
| 3943 measured reflections | l = −15→16 |
| 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.075 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.17P] where P = (Fo2 + 2Fc2)/3 |
| 1821 reflections | (Δ/σ)max = 0.004 |
| 111 parameters | Δρmax = 0.20 e Å−3 |
| 1 restraint | Δρmin = −0.16 e Å−3 |
| C10H8ClN | V = 850.38 (11) Å3 |
| Mr = 177.62 | Z = 4 |
| Orthorhombic, Pca21 | Mo Kα radiation |
| a = 12.7961 (9) Å | µ = 0.39 mm−1 |
| b = 5.0660 (4) Å | T = 173 K |
| c = 13.1181 (9) Å | 0.47 × 0.46 × 0.23 mm |
| Bruker SMART 1000 CCD diffractometer | 1821 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1703 reflections with I > 2σ(I) |
| Tmin = 0.840, Tmax = 0.917 | Rint = 0.016 |
| 3943 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 1 restraint |
| wR(F2) = 0.075 | H-atom parameters constrained |
| S = 1.09 | Δρmax = 0.20 e Å−3 |
| 1821 reflections | Δρmin = −0.16 e Å−3 |
| 111 parameters |
Experimental. MS (m/z):M+ 177. 1H NMR(CDCl3,400 MHz,delta dppm): 2.83(s,3H,CH3), 7.38(m,2H,quinoline 3,6-H), 7.80(d, J=7.2 Hz,1H, quinoline 7-H),8.03(d, J =8.0 Hz,1H,quinoline 5-H), 8.00(d,J = 8.4 Hz, 1H,quinoline 4-H) |
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 | ||
| Cl1 | 0.13075 (3) | −0.06692 (9) | −0.13065 (4) | 0.03616 (14) | |
| C1 | 0.33097 (14) | 0.5106 (4) | 0.00528 (15) | 0.0286 (4) | |
| C2 | 0.33961 (16) | 0.5667 (4) | 0.11114 (16) | 0.0336 (4) | |
| H2 | 0.3873 | 0.6971 | 0.1345 | 0.040* | |
| C3 | 0.27923 (15) | 0.4323 (3) | 0.17875 (15) | 0.0323 (4) | |
| H3 | 0.2846 | 0.4675 | 0.2497 | 0.039* | |
| C4 | 0.20807 (14) | 0.2386 (3) | 0.14243 (14) | 0.0277 (4) | |
| C5 | 0.14115 (15) | 0.0969 (4) | 0.20801 (15) | 0.0327 (4) | |
| H5 | 0.1427 | 0.1293 | 0.2793 | 0.039* | |
| C6 | 0.07432 (15) | −0.0864 (4) | 0.16908 (16) | 0.0349 (4) | |
| H6 | 0.0285 | −0.1792 | 0.2134 | 0.042* | |
| C7 | 0.07260 (15) | −0.1394 (4) | 0.06385 (16) | 0.0330 (4) | |
| H7 | 0.0266 | −0.2701 | 0.0377 | 0.040* | |
| C8 | 0.13698 (14) | −0.0033 (4) | −0.00123 (15) | 0.0271 (4) | |
| C9 | 0.20665 (13) | 0.1930 (3) | 0.03548 (13) | 0.0248 (3) | |
| C10 | 0.39634 (17) | 0.6615 (5) | −0.06992 (17) | 0.0393 (5) | |
| H10A | 0.4700 | 0.6137 | −0.0613 | 0.059* | |
| H10B | 0.3877 | 0.8513 | −0.0582 | 0.059* | |
| H10C | 0.3740 | 0.6181 | −0.1394 | 0.059* | |
| N1 | 0.26803 (12) | 0.3289 (3) | −0.03180 (11) | 0.0268 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0393 (2) | 0.0441 (3) | 0.0251 (2) | −0.00280 (19) | −0.0036 (2) | −0.0074 (2) |
| C1 | 0.0279 (9) | 0.0261 (8) | 0.0319 (10) | 0.0032 (7) | −0.0008 (8) | 0.0037 (7) |
| C2 | 0.0343 (10) | 0.0291 (10) | 0.0374 (11) | −0.0015 (8) | −0.0081 (8) | −0.0030 (8) |
| C3 | 0.0397 (10) | 0.0305 (9) | 0.0266 (9) | 0.0039 (8) | −0.0052 (8) | −0.0054 (7) |
| C4 | 0.0320 (9) | 0.0253 (9) | 0.0259 (9) | 0.0060 (7) | −0.0009 (7) | −0.0001 (7) |
| C5 | 0.0412 (10) | 0.0344 (10) | 0.0223 (9) | 0.0063 (8) | 0.0002 (8) | 0.0031 (7) |
| C6 | 0.0339 (10) | 0.0382 (11) | 0.0325 (10) | −0.0010 (8) | 0.0045 (8) | 0.0086 (8) |
| C7 | 0.0297 (9) | 0.0334 (10) | 0.0360 (10) | −0.0033 (8) | −0.0023 (8) | 0.0029 (8) |
| C8 | 0.0294 (9) | 0.0310 (8) | 0.0209 (9) | 0.0033 (7) | −0.0029 (7) | −0.0013 (7) |
| C9 | 0.0253 (8) | 0.0245 (8) | 0.0247 (9) | 0.0056 (7) | −0.0025 (7) | 0.0005 (6) |
| C10 | 0.0408 (10) | 0.0375 (10) | 0.0396 (12) | −0.0067 (10) | 0.0004 (9) | 0.0082 (9) |
| N1 | 0.0265 (7) | 0.0274 (7) | 0.0264 (8) | 0.0039 (6) | 0.0013 (6) | 0.0030 (6) |
| Cl1—C8 | 1.730 (2) | C5—H5 | 0.9500 |
| C1—N1 | 1.316 (3) | C6—C7 | 1.407 (3) |
| C1—C2 | 1.422 (3) | C6—H6 | 0.9500 |
| C1—C10 | 1.503 (3) | C7—C8 | 1.372 (3) |
| C2—C3 | 1.359 (3) | C7—H7 | 0.9500 |
| C2—H2 | 0.9500 | C8—C9 | 1.420 (3) |
| C3—C4 | 1.421 (2) | C9—N1 | 1.367 (2) |
| C3—H3 | 0.9500 | C10—H10A | 0.9800 |
| C4—C5 | 1.410 (3) | C10—H10B | 0.9800 |
| C4—C9 | 1.422 (2) | C10—H10C | 0.9800 |
| C5—C6 | 1.362 (3) | ||
| N1—C1—C2 | 123.25 (18) | C7—C6—H6 | 119.7 |
| N1—C1—C10 | 116.99 (18) | C8—C7—C6 | 120.36 (18) |
| C2—C1—C10 | 119.76 (18) | C8—C7—H7 | 119.8 |
| C3—C2—C1 | 119.55 (18) | C6—C7—H7 | 119.8 |
| C3—C2—H2 | 120.2 | C7—C8—C9 | 121.19 (18) |
| C1—C2—H2 | 120.2 | C7—C8—Cl1 | 119.30 (15) |
| C2—C3—C4 | 119.44 (18) | C9—C8—Cl1 | 119.49 (15) |
| C2—C3—H3 | 120.3 | N1—C9—C8 | 119.62 (16) |
| C4—C3—H3 | 120.3 | N1—C9—C4 | 123.21 (16) |
| C5—C4—C3 | 122.42 (17) | C8—C9—C4 | 117.16 (16) |
| C5—C4—C9 | 120.76 (17) | C1—C10—H10A | 109.5 |
| C3—C4—C9 | 116.82 (16) | C1—C10—H10B | 109.5 |
| C6—C5—C4 | 119.98 (18) | H10A—C10—H10B | 109.5 |
| C6—C5—H5 | 120.0 | C1—C10—H10C | 109.5 |
| C4—C5—H5 | 120.0 | H10A—C10—H10C | 109.5 |
| C5—C6—C7 | 120.54 (18) | H10B—C10—H10C | 109.5 |
| C5—C6—H6 | 119.7 | C1—N1—C9 | 117.70 (16) |
| N1—C1—C2—C3 | −1.4 (3) | Cl1—C8—C9—N1 | −0.1 (2) |
| C10—C1—C2—C3 | 179.05 (18) | C7—C8—C9—C4 | 1.1 (2) |
| C1—C2—C3—C4 | −0.3 (3) | Cl1—C8—C9—C4 | 179.55 (13) |
| C2—C3—C4—C5 | −178.29 (18) | C5—C4—C9—N1 | 178.44 (15) |
| C2—C3—C4—C9 | 1.5 (2) | C3—C4—C9—N1 | −1.4 (2) |
| C3—C4—C5—C6 | 179.90 (17) | C5—C4—C9—C8 | −1.2 (2) |
| C9—C4—C5—C6 | 0.1 (3) | C3—C4—C9—C8 | 178.99 (15) |
| C4—C5—C6—C7 | 1.1 (3) | C2—C1—N1—C9 | 1.5 (3) |
| C5—C6—C7—C8 | −1.2 (3) | C10—C1—N1—C9 | −178.87 (16) |
| C6—C7—C8—C9 | 0.1 (3) | C8—C9—N1—C1 | 179.50 (16) |
| C6—C7—C8—Cl1 | −178.36 (15) | C4—C9—N1—C1 | −0.1 (2) |
| C7—C8—C9—N1 | −178.55 (17) |
Experimental details
| Crystal data | |
| Chemical formula | C10H8ClN |
| Mr | 177.62 |
| Crystal system, space group | Orthorhombic, Pca21 |
| Temperature (K) | 173 |
| a, b, c (Å) | 12.7961 (9), 5.0660 (4), 13.1181 (9) |
| V (Å3) | 850.38 (11) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.39 |
| Crystal size (mm) | 0.47 × 0.46 × 0.23 |
| Data collection | |
| Diffractometer | Bruker SMART 1000 CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
| Tmin, Tmax | 0.840, 0.917 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3943, 1821, 1703 |
| Rint | 0.016 |
| (sin θ/λ)max (Å−1) | 0.640 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.075, 1.09 |
| No. of reflections | 1821 |
| No. of parameters | 111 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.20, −0.16 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was funded by the SIT program of Hunan University (2008).
References
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lee, D.-Y. & Hartwig, J.-F. (2005). Org. Lett. 7, 1169–1172. Web of Science CrossRef PubMed CAS Google Scholar
Ranu, B. C., Hajra, A. & Jana, U. (2000). Tetrahedron Lett. 41. 531–533. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, Q.-L. & Hartwig, F. (2006). J. Am. Chem. Soc. 128, 10028–10029. Web of Science CSD CrossRef PubMed CAS Google Scholar
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The structure of the title compound, 8-chloro-2-methylquinoline, is shown in Fig 1. It is an important intermediate of medecine industry (Shen et al., 2006; Ranu et al., 2000; Lee et al., 2005). The crystal packing shows π-π stacking between the N containing aromatic ring and the aromatic ring with the chloro substituent with a centroid-centroid distance of 3.819Å.