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access5-(5-Bromo-2-methoxyphenyl)-2-fluoropyridine
aDepartment of Chemistry, Gomal University, Dera Ismail Khan, K.P.K., Pakistan, and bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
*Correspondence e-mail: dmntahir_uos@yahoo.com
In the title compound, C12H9BrFNO, the dihedral angle between the aromatic rings is 51.39 (5)°; the C atom of the methoxy group is close to being coplanar with its attached ring (r.m.s. deviation = 0.0172 Å] and is oriented away from the pyridine ring. In the crystal, molecules interact by van der Waals forces.
Related literature
For a related structure, see: Adeel et al. (2012![[Adeel, M., Elahi, F., Tahir, M. N., Khan, A. & Langer, P. (2012). Acta Cryst. E68, o2043.]](../../../../../../logos/arrows/e_arr.gif "Adeel, M., Elahi, F., Tahir, M. N., Khan, A. & Langer, P. (2012). Acta Cryst. E68, o2043.")
); Elahi et al. (2012a,b); Elahi et al. (2012).
![[Scheme 1]](hb6919scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON.
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536812034435/hb6919sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812034435/hb6919Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812034435/hb6919Isup3.cml
To a 6 ml solution of 5-bromo-2-fluoropyridine (0.20 g, 1.13 mmol), 5-bromo-2-methoxyphenylboronic acid (0.314 g, 1.36 mmol) in dioxane and K3PO4 (0.361 g, 1.7 mmol, in 1 ml H2O) was added Pd(PPh3)4 (1.5 mole %) at 373 K under N2 atmosphere. The reaction mixture was refluxed for 8 h. Then 20 ml of distilled water was added. The aqueous layer was extracted three times with EtOAc(3 × 15 ml). The organic layer was evaporated in vacuo and the crude product was obtained. Colorless needles of (I) were obtained by the recrystalization of crude product in a saturated CHCl3/CH3OH solution.
Yield: 0.294 g, 92%. m.p. 345–347 K.
The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = xUeq(C), where x = 1.5 for methyl and x = 1.2 for other H-atoms.
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
![[Figure 1]](./hb6919fig1thm.gif) | Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. |
| C12H9BrFNO | F(000) = 560 |
| Mr = 282.11 | Dx = 1.714 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1441 reflections |
| a = 3.9376 (4) Å | θ = 1.8–25.5° |
| b = 20.999 (3) Å | µ = 3.75 mm−1 |
| c = 13.2700 (15) Å | T = 296 K |
| β = 95.035 (7)° | Needle, colorless |
| V = 1093.0 (2) Å3 | 0.34 × 0.18 × 0.16 mm |
| Z = 4 |
| Bruker Kappa APEXII CCD diffractometer | 2027 independent reflections |
| Radiation source: fine-focus sealed tube | 1441 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.042 |
| Detector resolution: 8.10 pixels mm-1 | θmax = 25.5°, θmin = 1.8° |
| ω scans | h = −4→4 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −25→15 |
| Tmin = 0.674, Tmax = 0.698 | l = −15→16 |
| 7773 measured reflections |
| 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.068 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.027P)2] where P = (Fo2 + 2Fc2)/3 |
| 2027 reflections | (Δ/σ)max = 0.001 |
| 146 parameters | Δρmax = 0.29 e Å−3 |
| 0 restraints | Δρmin = −0.28 e Å−3 |
| C12H9BrFNO | V = 1093.0 (2) Å3 |
| Mr = 282.11 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 3.9376 (4) Å | µ = 3.75 mm−1 |
| b = 20.999 (3) Å | T = 296 K |
| c = 13.2700 (15) Å | 0.34 × 0.18 × 0.16 mm |
| β = 95.035 (7)° |
| Bruker Kappa APEXII CCD diffractometer | 2027 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1441 reflections with I > 2σ(I) |
| Tmin = 0.674, Tmax = 0.698 | Rint = 0.042 |
| 7773 measured reflections |
| R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
| wR(F2) = 0.068 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.29 e Å−3 |
| 2027 reflections | Δρmin = −0.28 e Å−3 |
| 146 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | 0.56028 (8) | 0.42649 (2) | 0.65535 (3) | 0.0533 (1) | |
| F1 | 0.6238 (6) | 0.43194 (10) | −0.01878 (15) | 0.0815 (9) | |
| O1 | 1.0021 (5) | 0.25300 (10) | 0.32894 (14) | 0.0422 (7) | |
| N1 | 0.5368 (7) | 0.35827 (13) | 0.0979 (2) | 0.0501 (11) | |
| C1 | 0.7736 (7) | 0.35084 (13) | 0.3789 (2) | 0.0326 (10) | |
| C2 | 0.9046 (7) | 0.29045 (14) | 0.4060 (2) | 0.0337 (10) | |
| C3 | 0.9321 (7) | 0.27195 (15) | 0.5063 (2) | 0.0407 (11) | |
| C4 | 0.8285 (7) | 0.31185 (16) | 0.5803 (3) | 0.0439 (11) | |
| C5 | 0.7032 (7) | 0.37101 (14) | 0.5544 (2) | 0.0377 (11) | |
| C6 | 0.6760 (7) | 0.39044 (14) | 0.4547 (2) | 0.0378 (10) | |
| C7 | 1.1517 (8) | 0.19256 (15) | 0.3560 (3) | 0.0511 (12) | |
| C8 | 0.7416 (7) | 0.37357 (13) | 0.2724 (2) | 0.0333 (10) | |
| C9 | 0.8664 (7) | 0.43295 (15) | 0.2473 (2) | 0.0429 (11) | |
| C10 | 0.8273 (8) | 0.45436 (16) | 0.1482 (3) | 0.0510 (11) | |
| C11 | 0.6638 (9) | 0.41379 (17) | 0.0803 (3) | 0.0516 (12) | |
| C12 | 0.5761 (7) | 0.33878 (15) | 0.1936 (2) | 0.0418 (11) | |
| H3 | 1.02142 | 0.23212 | 0.52415 | 0.0488* | |
| H4 | 0.84380 | 0.29866 | 0.64746 | 0.0525* | |
| H6 | 0.59073 | 0.43076 | 0.43811 | 0.0454* | |
| H7A | 1.23508 | 0.17326 | 0.29741 | 0.0763* | |
| H7B | 0.98311 | 0.16542 | 0.38171 | 0.0763* | |
| H7C | 1.33727 | 0.19847 | 0.40709 | 0.0763* | |
| H9 | 0.97674 | 0.45841 | 0.29733 | 0.0514* | |
| H10 | 0.90758 | 0.49388 | 0.12940 | 0.0611* | |
| H12 | 0.48683 | 0.29927 | 0.20876 | 0.0503* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0574 (2) | 0.0553 (2) | 0.0484 (2) | −0.0061 (2) | 0.0108 (2) | −0.0154 (2) |
| F1 | 0.138 (2) | 0.0654 (14) | 0.0405 (13) | 0.0176 (14) | 0.0042 (12) | 0.0153 (12) |
| O1 | 0.0590 (13) | 0.0327 (12) | 0.0339 (13) | 0.0100 (11) | −0.0007 (10) | 0.0006 (11) |
| N1 | 0.0724 (19) | 0.0421 (18) | 0.0340 (18) | 0.0103 (16) | −0.0060 (14) | 0.0015 (15) |
| C1 | 0.0329 (16) | 0.0309 (17) | 0.0330 (19) | −0.0033 (14) | −0.0023 (14) | 0.0005 (15) |
| C2 | 0.0343 (16) | 0.0343 (17) | 0.0316 (19) | −0.0043 (15) | −0.0022 (14) | −0.0027 (16) |
| C3 | 0.0501 (18) | 0.0339 (18) | 0.037 (2) | −0.0014 (16) | −0.0026 (15) | 0.0062 (16) |
| C4 | 0.0507 (19) | 0.048 (2) | 0.0316 (19) | −0.0100 (17) | −0.0040 (15) | 0.0046 (17) |
| C5 | 0.0379 (17) | 0.0410 (19) | 0.034 (2) | −0.0041 (15) | 0.0014 (14) | −0.0062 (16) |
| C6 | 0.0371 (17) | 0.0322 (17) | 0.043 (2) | −0.0003 (15) | −0.0025 (14) | −0.0026 (17) |
| C7 | 0.059 (2) | 0.040 (2) | 0.053 (2) | 0.0107 (17) | −0.0028 (17) | −0.0056 (18) |
| C8 | 0.0343 (16) | 0.0294 (17) | 0.0362 (19) | 0.0064 (14) | 0.0028 (14) | 0.0004 (15) |
| C9 | 0.0474 (18) | 0.0372 (19) | 0.043 (2) | −0.0009 (16) | −0.0016 (15) | −0.0009 (18) |
| C10 | 0.065 (2) | 0.0376 (19) | 0.051 (2) | 0.0003 (18) | 0.0087 (18) | 0.0078 (19) |
| C11 | 0.071 (2) | 0.050 (2) | 0.034 (2) | 0.021 (2) | 0.0063 (17) | 0.0084 (19) |
| C12 | 0.0521 (19) | 0.0320 (18) | 0.040 (2) | 0.0030 (16) | −0.0033 (16) | −0.0003 (17) |
| Br1—C5 | 1.898 (3) | C8—C9 | 1.391 (4) |
| F1—C11 | 1.365 (4) | C8—C12 | 1.390 (4) |
| O1—C2 | 1.371 (3) | C9—C10 | 1.386 (5) |
| O1—C7 | 1.432 (4) | C10—C11 | 1.360 (5) |
| N1—C11 | 1.298 (5) | C3—H3 | 0.9300 |
| N1—C12 | 1.330 (4) | C4—H4 | 0.9300 |
| C1—C2 | 1.404 (4) | C6—H6 | 0.9300 |
| C1—C6 | 1.385 (4) | C7—H7A | 0.9600 |
| C1—C8 | 1.487 (4) | C7—H7B | 0.9600 |
| C2—C3 | 1.382 (4) | C7—H7C | 0.9600 |
| C3—C4 | 1.380 (5) | C9—H9 | 0.9300 |
| C4—C5 | 1.369 (4) | C10—H10 | 0.9300 |
| C5—C6 | 1.380 (4) | C12—H12 | 0.9300 |
| C2—O1—C7 | 117.2 (2) | N1—C11—C10 | 127.7 (4) |
| C11—N1—C12 | 115.7 (3) | N1—C12—C8 | 124.3 (3) |
| C2—C1—C6 | 118.4 (2) | C2—C3—H3 | 120.00 |
| C2—C1—C8 | 122.2 (2) | C4—C3—H3 | 120.00 |
| C6—C1—C8 | 119.5 (2) | C3—C4—H4 | 120.00 |
| O1—C2—C1 | 116.6 (2) | C5—C4—H4 | 120.00 |
| O1—C2—C3 | 123.6 (3) | C1—C6—H6 | 119.00 |
| C1—C2—C3 | 119.8 (3) | C5—C6—H6 | 119.00 |
| C2—C3—C4 | 120.8 (3) | O1—C7—H7A | 109.00 |
| C3—C4—C5 | 119.7 (3) | O1—C7—H7B | 109.00 |
| Br1—C5—C4 | 120.2 (2) | O1—C7—H7C | 109.00 |
| Br1—C5—C6 | 119.5 (2) | H7A—C7—H7B | 109.00 |
| C4—C5—C6 | 120.3 (3) | H7A—C7—H7C | 109.00 |
| C1—C6—C5 | 121.0 (3) | H7B—C7—H7C | 109.00 |
| C1—C8—C9 | 120.9 (2) | C8—C9—H9 | 120.00 |
| C1—C8—C12 | 122.8 (2) | C10—C9—H9 | 120.00 |
| C9—C8—C12 | 116.3 (2) | C9—C10—H10 | 122.00 |
| C8—C9—C10 | 120.4 (3) | C11—C10—H10 | 122.00 |
| C9—C10—C11 | 115.6 (3) | N1—C12—H12 | 118.00 |
| F1—C11—N1 | 114.2 (3) | C8—C12—H12 | 118.00 |
| F1—C11—C10 | 118.1 (3) | ||
| C7—O1—C2—C1 | 177.0 (2) | O1—C2—C3—C4 | −179.8 (3) |
| C7—O1—C2—C3 | −2.4 (4) | C1—C2—C3—C4 | 0.8 (4) |
| C12—N1—C11—F1 | 179.1 (3) | C2—C3—C4—C5 | −1.3 (4) |
| C12—N1—C11—C10 | −0.9 (5) | C3—C4—C5—Br1 | −179.9 (2) |
| C11—N1—C12—C8 | −0.3 (5) | C3—C4—C5—C6 | 0.9 (4) |
| C6—C1—C2—O1 | −179.2 (2) | Br1—C5—C6—C1 | −179.1 (2) |
| C6—C1—C2—C3 | 0.2 (4) | C4—C5—C6—C1 | 0.1 (4) |
| C8—C1—C2—O1 | −0.1 (4) | C1—C8—C9—C10 | −178.3 (3) |
| C8—C1—C2—C3 | 179.3 (3) | C12—C8—C9—C10 | −0.8 (4) |
| C2—C1—C6—C5 | −0.6 (4) | C1—C8—C12—N1 | 178.6 (3) |
| C8—C1—C6—C5 | −179.8 (3) | C9—C8—C12—N1 | 1.1 (4) |
| C2—C1—C8—C9 | −130.1 (3) | C8—C9—C10—C11 | −0.2 (4) |
| C2—C1—C8—C12 | 52.6 (4) | C9—C10—C11—F1 | −178.8 (3) |
| C6—C1—C8—C9 | 49.0 (4) | C9—C10—C11—N1 | 1.2 (5) |
| C6—C1—C8—C12 | −128.3 (3) |
Experimental details
| Crystal data | |
| Chemical formula | C12H9BrFNO |
| Mr | 282.11 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 296 |
| a, b, c (Å) | 3.9376 (4), 20.999 (3), 13.2700 (15) |
| β (°) | 95.035 (7) |
| V (Å3) | 1093.0 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 3.75 |
| Crystal size (mm) | 0.34 × 0.18 × 0.16 |
| Data collection | |
| Diffractometer | Bruker Kappa APEXII CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
| Tmin, Tmax | 0.674, 0.698 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7773, 2027, 1441 |
| Rint | 0.042 |
| (sin θ/λ)max (Å−1) | 0.606 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.068, 1.04 |
| No. of reflections | 2027 |
| No. of parameters | 146 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.29, −0.28 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Acknowledgements
The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. MA also acknowledges the World University Service, Germany, for an equipment grant and the Higher Education Commission, Pakistan, for a resource grant.
References
Adeel, M., Elahi, F., Tahir, M. N., Khan, A. & Langer, P. (2012). Acta Cryst. E68, o2043. CSD CrossRef IUCr Journals Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elahi, F., Adeel, M. & Tahir, M. N. (2012a). Acta Cryst. E68, o2124. CSD CrossRef IUCr Journals Google Scholar
Elahi, F., Adeel, M. & Tahir, M. N. (2012b). Acta Cryst. E68, o2180. CSD CrossRef IUCr Journals Google Scholar
Elahi, F., Adeel, M., Tahir, M. N., Langer, P. & Ahmad, S. (2012). Acta Cryst. E68, o2070. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
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Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
We have reported the crystal structure of 5-(4-chlorophenyl)-2-fluoropyridine (Adeel et al., 2012), 4-(2-fluoropyridin-5-yl)phenol (Elahi et al., 2012a), 5-(2,3-dichlorophenyl)-2-fluoropyridine (Elahi et al., 2012b) and 2-fluoro-5-(4-fluorophenyl)pyridine (Elahi et al., 2012) which have common moiety of 2-fluoropyridine as in the title compound, (Fig. 1).
In the title compound, the 1-bromo-4-methoxybenzene A (C1–C7/BR1/O1) and the 2-fluoropyridine B (C8—C12/N1/F1) systems are almost planar with r.m.s. deviations of 0.0172 Å and 0.0087 Å, respectively. The dihedral angle between A/B is 51.39 (5)°. There does not exist any kind of H-bonding and the molecules interact by van der Waals forces.