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access8-Bromo-2-methylquinoline
aCollege of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China
*Correspondence e-mail: axhu0731@yahoo.com.cn
In the of the title compound, C10H8BrN, the dihedral angle between the two six-membered rings of the quinoline system is 0.49 (16)°. The molecules are packed in a face-to-face arrangement fashion, with a centroid–centroid distance of 3.76 Å between the benzene and pyridine rings of adjacent molecules. No hydrogen bonding is found in the crystal structure.
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). For related structures, see: Amini et al. (2008); Fazaeli et al. (2008); Sattarzadeh et al. (2009).
![[Scheme 1]](xu2533scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2003); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809020625/xu2533sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809020625/xu2533Isup2.hkl
A solution of 2-bromoaniline (0.05 mol), boric acid (3.10 g) and 18% HCl (50 ml) was heated to reflux. Then a mixture of crotonaldehyde (0.06 mol) and 2-bromonitrobenzene (0.01 mol) was slowly added with stirring in 1 h. The reaction mixture was subsequently stirred at 373 K for another 2.5 h, and then an equimolar amount of anhydrous ZnCl2 was added with vigorous stirring for 0.5 h. After the reaction was completed, the reaction solution was cooled in an ice bath and the crude brown solid was filtered, washed with 2-propanol, dissolved in the water, and neutralized with concentrated NH3.H2O solution to pH of 8. After cool immersed, filtrated and air dried, the product was obtained as a grey solid. Yield: 52.0%. m.p. 342–343 K. Crystals suitable for X-ray were obtained by slow evaporation of an ethanol solution at room temperature.
The H-atoms were positioned geometrically, with C—H = 0.93 Å for aromatic, 0.96 Å for methyl, and refined as riding with Uiso(H) = 1.2 or 1.5 Ueq(C).
Data collection: SMART (Bruker, 2003); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2533fig1thm.gif)
| C10H8BrN | F(000) = 440 |
| Mr = 222.08 | Dx = 1.636 Mg m−3 |
| Monoclinic, P21/c | Melting point: 343 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.0440 (17) Å | Cell parameters from 1765 reflections |
| b = 13.467 (4) Å | θ = 2.2–26.0° |
| c = 13.391 (4) Å | µ = 4.50 mm−1 |
| β = 97.678 (4)° | T = 291 K |
| V = 901.4 (5) Å3 | Block, colourless |
| Z = 4 | 0.36 × 0.31 × 0.28 mm |
| Bruker SMART APEX CCD diffractometer | 1765 independent reflections |
| Radiation source: fine-focus sealed tube | 1039 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.156 |
| ϕ and ω scans | θmax = 26.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −6→6 |
| Tmin = 0.235, Tmax = 0.286 | k = −13→16 |
| 4668 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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.195 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0989P)2] where P = (Fo2 + 2Fc2)/3 |
| 1765 reflections | (Δ/σ)max < 0.001 |
| 110 parameters | Δρmax = 0.88 e Å−3 |
| 0 restraints | Δρmin = −0.91 e Å−3 |
| C10H8BrN | V = 901.4 (5) Å3 |
| Mr = 222.08 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 5.0440 (17) Å | µ = 4.50 mm−1 |
| b = 13.467 (4) Å | T = 291 K |
| c = 13.391 (4) Å | 0.36 × 0.31 × 0.28 mm |
| β = 97.678 (4)° |
| Bruker SMART APEX CCD diffractometer | 1765 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1039 reflections with I > 2σ(I) |
| Tmin = 0.235, Tmax = 0.286 | Rint = 0.156 |
| 4668 measured reflections |
| R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
| wR(F2) = 0.195 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.88 e Å−3 |
| 1765 reflections | Δρmin = −0.91 e Å−3 |
| 110 parameters |
Experimental. 1H NMR (CDCl3, 400 MHz) δ: 2.82 (s, 3H, CH3), 7.33(m, 2H, quinoline 3,6-H), 7.73 (dd, J=8.0 Hz, J=1.2 Hz, 1H, quinoline 7-H), 8.02 (m, 2H, quinoline 4,5-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 | ||
| Br1 | 1.04425 (17) | 0.41478 (5) | 0.40291 (5) | 0.0783 (4) | |
| N1 | 0.6713 (11) | 0.2556 (3) | 0.2991 (3) | 0.0507 (12) | |
| C1 | 0.9974 (14) | 0.3782 (4) | 0.2655 (4) | 0.0536 (16) | |
| C8 | 0.8122 (12) | 0.3021 (4) | 0.2325 (4) | 0.0429 (13) | |
| C9 | 0.7845 (13) | 0.2775 (4) | 0.1287 (4) | 0.0517 (15) | |
| C7 | 0.5039 (14) | 0.1846 (4) | 0.2646 (5) | 0.0568 (16) | |
| C2 | 1.1397 (14) | 0.4256 (4) | 0.2022 (6) | 0.0586 (16) | |
| H2 | 1.2578 | 0.4757 | 0.2266 | 0.070* | |
| C5 | 0.6014 (14) | 0.2003 (5) | 0.0957 (5) | 0.0643 (18) | |
| H5 | 0.5778 | 0.1807 | 0.0285 | 0.077* | |
| C3 | 1.1122 (15) | 0.4004 (5) | 0.0989 (5) | 0.0621 (18) | |
| H3 | 1.2156 | 0.4321 | 0.0561 | 0.074* | |
| C6 | 0.4624 (16) | 0.1559 (5) | 0.1622 (5) | 0.070 (2) | |
| H6 | 0.3394 | 0.1064 | 0.1408 | 0.084* | |
| C4 | 0.9318 (15) | 0.3287 (5) | 0.0624 (5) | 0.068 (2) | |
| H4 | 0.9066 | 0.3138 | −0.0061 | 0.082* | |
| C10 | 0.3468 (14) | 0.1364 (5) | 0.3370 (6) | 0.0694 (19) | |
| H10A | 0.3969 | 0.0677 | 0.3444 | 0.104* | |
| H10B | 0.1596 | 0.1412 | 0.3123 | 0.104* | |
| H10C | 0.3821 | 0.1690 | 0.4011 | 0.104* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.1139 (9) | 0.0735 (6) | 0.0436 (4) | −0.0082 (4) | −0.0042 (4) | −0.0114 (3) |
| N1 | 0.059 (3) | 0.050 (3) | 0.042 (3) | 0.011 (3) | 0.004 (2) | 0.005 (2) |
| C1 | 0.074 (5) | 0.044 (3) | 0.040 (3) | 0.005 (3) | −0.001 (3) | −0.001 (2) |
| C8 | 0.037 (3) | 0.050 (3) | 0.040 (3) | 0.012 (3) | 0.001 (2) | −0.001 (2) |
| C9 | 0.054 (4) | 0.063 (3) | 0.037 (3) | 0.009 (3) | 0.002 (3) | −0.001 (3) |
| C7 | 0.059 (4) | 0.053 (3) | 0.059 (4) | 0.011 (3) | 0.009 (3) | 0.007 (3) |
| C2 | 0.051 (4) | 0.055 (3) | 0.070 (4) | 0.002 (3) | 0.010 (3) | 0.004 (3) |
| C5 | 0.057 (5) | 0.083 (4) | 0.050 (4) | 0.003 (4) | −0.006 (3) | −0.015 (3) |
| C3 | 0.054 (5) | 0.073 (4) | 0.063 (4) | 0.004 (4) | 0.021 (3) | 0.013 (3) |
| C6 | 0.080 (6) | 0.063 (4) | 0.062 (4) | −0.002 (4) | −0.008 (4) | −0.007 (3) |
| C4 | 0.081 (6) | 0.085 (5) | 0.039 (3) | 0.013 (4) | 0.012 (3) | 0.004 (3) |
| C10 | 0.054 (4) | 0.068 (4) | 0.088 (5) | 0.002 (4) | 0.015 (4) | 0.007 (4) |
| Br1—C1 | 1.889 (6) | C2—H2 | 0.9300 |
| N1—C7 | 1.318 (8) | C5—C6 | 1.344 (10) |
| N1—C8 | 1.365 (7) | C5—H5 | 0.9300 |
| C1—C2 | 1.344 (9) | C3—C4 | 1.371 (10) |
| C1—C8 | 1.416 (8) | C3—H3 | 0.9300 |
| C8—C9 | 1.418 (7) | C6—H6 | 0.9300 |
| C9—C4 | 1.411 (9) | C4—H4 | 0.9300 |
| C9—C5 | 1.422 (9) | C10—H10A | 0.9600 |
| C7—C6 | 1.414 (8) | C10—H10B | 0.9600 |
| C7—C10 | 1.481 (9) | C10—H10C | 0.9600 |
| C2—C3 | 1.412 (10) | ||
| C7—N1—C8 | 118.0 (5) | C6—C5—H5 | 120.2 |
| C2—C1—C8 | 122.1 (6) | C9—C5—H5 | 120.2 |
| C2—C1—Br1 | 118.9 (5) | C4—C3—C2 | 119.5 (6) |
| C8—C1—Br1 | 119.0 (4) | C4—C3—H3 | 120.2 |
| N1—C8—C1 | 120.5 (5) | C2—C3—H3 | 120.2 |
| N1—C8—C9 | 122.8 (5) | C5—C6—C7 | 119.9 (7) |
| C1—C8—C9 | 116.7 (5) | C5—C6—H6 | 120.1 |
| C4—C9—C8 | 120.8 (6) | C7—C6—H6 | 120.1 |
| C4—C9—C5 | 122.4 (6) | C3—C4—C9 | 119.9 (6) |
| C8—C9—C5 | 116.8 (5) | C3—C4—H4 | 120.1 |
| N1—C7—C6 | 122.9 (6) | C9—C4—H4 | 120.1 |
| N1—C7—C10 | 117.6 (6) | C7—C10—H10A | 109.5 |
| C6—C7—C10 | 119.5 (7) | C7—C10—H10B | 109.5 |
| C1—C2—C3 | 120.9 (6) | H10A—C10—H10B | 109.5 |
| C1—C2—H2 | 119.6 | C7—C10—H10C | 109.5 |
| C3—C2—H2 | 119.6 | H10A—C10—H10C | 109.5 |
| C6—C5—C9 | 119.6 (6) | H10B—C10—H10C | 109.5 |
Experimental details
| Crystal data | |
| Chemical formula | C10H8BrN |
| Mr | 222.08 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 291 |
| a, b, c (Å) | 5.0440 (17), 13.467 (4), 13.391 (4) |
| β (°) | 97.678 (4) |
| V (Å3) | 901.4 (5) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 4.50 |
| Crystal size (mm) | 0.36 × 0.31 × 0.28 |
| Data collection | |
| Diffractometer | Bruker SMART APEX CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
| Tmin, Tmax | 0.235, 0.286 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4668, 1765, 1039 |
| Rint | 0.156 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.195, 1.01 |
| No. of reflections | 1765 |
| No. of parameters | 110 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.88, −0.91 |
Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Acknowledgements
This work was funded by the SIT program of Hunan University, China (2008).
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The title compound, 8-bromo-2-methylquinoline, is an important intermediate of medcine industry (Shen & Hartwig, 2006; Ranu et al., 2000; Lee & Hartwig, 2005). The unit-cell of the title compound contains four molecules, and the corresponding bond lengths and angles of these molecules are agree with each other. The molecules are stablizated by π-π stacking (centroids distance is 3.76 Å). Herein we report the synthesis and crystal structure of 8-bromo-2-methylquinoline. For more related structures, see: Amini et al.(2008), Fazaeli et al. (2008), Sattarzadeh et al. (2009).