Acta Cryst. (2009). E65, o134 [ doi:10.1107/S1600536808042104 ]
The title compound, C8H8BrNO2, does not show any significant intermolecular ![[pi]](/logos/entities/pi_rmgif.gif)
- or C-H
interactions in the crystal packing except for one weak BrBr [3.715 (1) Å] interaction.
The title compound, (I) was prepared by a method reported in literature (Oila et al., 2005) with some modification. The crystals were obtained by dissolving I (0.2 g) in methanol (50 ml) and evaporating the solvent slowly at room temperature for about 3 d.
H atoms were positioned geometrically, with O—H = 0.82 and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C/O), where x = 1.2 for aromatic H and x = 1.5 for other H.
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./lx2083fig1thm.gif)
| Fig. 1. A drawing of the title molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./lx2083fig2thm.gif)
| Fig. 2. Br···Br interaction in the title compound. [Symmetry code: (i) -x+1, y+1/2, -z+1/2.] |
| C8H8BrNO2 | F(000) = 456 |
| Mr = 230.06 | Dx = 1.715 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
| a = 18.518 (4) Å | θ = 10–14° |
| b = 4.1040 (8) Å | µ = 4.57 mm−1 |
| c = 12.442 (3) Å | T = 293 K |
| β = 109.52 (3)° | Block, colorless |
| V = 891.2 (4) Å3 | 0.20 × 0.10 × 0.10 mm |
| Z = 4 |
| Enraf–Nonius CAD-4 diffractometer | 975 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.0000 |
| graphite | θmax = 25.3°, θmin = 1.2° |
| ω/2θ scans | h = −22→20 |
| Absorption correction: ψ scan (North et al., 1968) | k = 0→4 |
| Tmin = 0.462, Tmax = 0.658 | l = 0→14 |
| 1602 measured reflections | 3 standard reflections every 200 reflections |
| 1602 independent reflections | intensity decay: 1% |
| 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)] = 0.061 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.066 | H-atom parameters constrained |
| S = 1.75 | w = 1/[σ2(Fo2)] |
| 1602 reflections | (Δ/σ)max < 0.000 |
| 110 parameters | Δρmax = 0.53 e Å−3 |
| 0 restraints | Δρmin = −0.61 e Å−3 |
| C8H8BrNO2 | V = 891.2 (4) Å3 |
| Mr = 230.06 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 18.518 (4) Å | µ = 4.57 mm−1 |
| b = 4.1040 (8) Å | T = 293 K |
| c = 12.442 (3) Å | 0.20 × 0.10 × 0.10 mm |
| β = 109.52 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 975 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.0000 |
| Tmin = 0.462, Tmax = 0.658 | θmax = 25.3° |
| 1602 measured reflections | 3 standard reflections every 200 reflections |
| 1602 independent reflections | intensity decay: 1% |
| R[F2 > 2σ(F2)] = 0.061 | H-atom parameters constrained |
| wR(F2) = 0.066 | Δρmax = 0.53 e Å−3 |
| S = 1.75 | Δρmin = −0.61 e Å−3 |
| 1602 reflections | Absolute structure: ? |
| 110 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
| Br | 0.41815 (4) | 0.6507 (2) | 0.25731 (6) | 0.0546 (3) | |
| O1 | 0.0882 (2) | −0.1451 (13) | 0.2125 (3) | 0.0691 (16) | |
| O2 | 0.1349 (2) | −0.0435 (11) | 0.3986 (4) | 0.0533 (15) | |
| N | 0.2635 (3) | 0.2009 (15) | 0.3797 (4) | 0.0450 (17) | |
| C1 | 0.3893 (3) | 0.4149 (17) | 0.4811 (4) | 0.067 (2) | |
| H1A | 0.3707 | 0.3787 | 0.5434 | 0.101* | |
| H1B | 0.4059 | 0.6370 | 0.4822 | 0.101* | |
| H1C | 0.4317 | 0.2717 | 0.4882 | 0.101* | |
| C2 | 0.3260 (3) | 0.3477 (18) | 0.3698 (5) | 0.0344 (16) | |
| C3 | 0.3290 (3) | 0.4444 (16) | 0.2646 (5) | 0.039 (2) | |
| C4 | 0.2680 (3) | 0.3789 (19) | 0.1651 (5) | 0.059 (2) | |
| H4A | 0.2702 | 0.4358 | 0.0939 | 0.071* | |
| C5 | 0.2053 (3) | 0.2298 (18) | 0.1755 (5) | 0.050 (2) | |
| H5A | 0.1632 | 0.1866 | 0.1109 | 0.060* | |
| C6 | 0.2038 (3) | 0.1425 (19) | 0.2814 (5) | 0.0426 (18) | |
| C7 | 0.1372 (4) | −0.0335 (18) | 0.2958 (6) | 0.050 (2) | |
| C8 | 0.0676 (3) | −0.1896 (19) | 0.4127 (5) | 0.070 (2) | |
| H8A | 0.0724 | −0.1875 | 0.4920 | 0.104* | |
| H8B | 0.0627 | −0.4104 | 0.3857 | 0.104* | |
| H8C | 0.0230 | −0.0679 | 0.3698 | 0.104* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br | 0.0482 (4) | 0.0590 (5) | 0.0589 (5) | −0.0020 (6) | 0.0211 (3) | 0.0028 (6) |
| O1 | 0.048 (3) | 0.092 (4) | 0.055 (4) | −0.011 (4) | 0.001 (3) | −0.013 (4) |
| O2 | 0.043 (3) | 0.070 (4) | 0.046 (3) | −0.007 (3) | 0.013 (2) | −0.002 (3) |
| N | 0.029 (3) | 0.065 (5) | 0.033 (3) | −0.006 (4) | 0.000 (3) | 0.004 (4) |
| C1 | 0.056 (4) | 0.087 (7) | 0.043 (4) | −0.027 (5) | −0.004 (4) | 0.012 (5) |
| C2 | 0.026 (4) | 0.031 (4) | 0.035 (4) | −0.003 (4) | −0.004 (3) | −0.004 (5) |
| C3 | 0.034 (4) | 0.045 (6) | 0.040 (4) | 0.002 (4) | 0.014 (4) | 0.009 (4) |
| C4 | 0.049 (4) | 0.088 (7) | 0.033 (4) | 0.004 (6) | 0.005 (4) | 0.031 (5) |
| C5 | 0.038 (4) | 0.076 (7) | 0.029 (4) | 0.001 (4) | 0.002 (3) | 0.002 (4) |
| C6 | 0.025 (4) | 0.060 (5) | 0.042 (4) | 0.004 (5) | 0.011 (3) | −0.001 (5) |
| C7 | 0.037 (5) | 0.060 (6) | 0.043 (5) | 0.004 (4) | 0.000 (4) | −0.010 (5) |
| C8 | 0.051 (4) | 0.079 (7) | 0.089 (5) | −0.011 (5) | 0.037 (4) | 0.010 (6) |
| Br—Bri | 3.715 (1) | C2—C3 | 1.387 (6) |
| Br—C3 | 1.884 (5) | C3—C4 | 1.396 (6) |
| O1—C7 | 1.218 (6) | C4—C5 | 1.356 (7) |
| O2—C7 | 1.294 (6) | C4—H4A | 0.9300 |
| O2—C8 | 1.446 (6) | C5—C6 | 1.375 (7) |
| N—C2 | 1.347 (6) | C5—H5A | 0.9300 |
| N—C6 | 1.368 (6) | C6—C7 | 1.491 (8) |
| C1—C2 | 1.510 (6) | C8—H8A | 0.9600 |
| C1—H1A | 0.9600 | C8—H8B | 0.9600 |
| C1—H1B | 0.9600 | C8—H8C | 0.9600 |
| C1—H1C | 0.9600 | ||
| C7—O2—C8 | 116.6 (5) | C3—C4—H4A | 121.0 |
| C2—N—C6 | 117.3 (5) | C4—C5—C6 | 120.0 (6) |
| C2—C1—H1A | 109.5 | C4—C5—H5A | 120.0 |
| C2—C1—H1B | 109.5 | C6—C5—H5A | 120.0 |
| H1A—C1—H1B | 109.5 | N—C6—C5 | 122.9 (6) |
| C2—C1—H1C | 109.5 | N—C6—C7 | 115.5 (6) |
| H1A—C1—H1C | 109.5 | C5—C6—C7 | 121.6 (6) |
| H1B—C1—H1C | 109.5 | O1—C7—O2 | 124.6 (7) |
| N—C2—C3 | 121.4 (5) | O1—C7—C6 | 119.4 (7) |
| N—C2—C1 | 115.2 (5) | O2—C7—C6 | 115.9 (6) |
| C3—C2—C1 | 123.3 (6) | O2—C8—H8A | 109.5 |
| C4—C3—C2 | 120.4 (5) | O2—C8—H8B | 109.5 |
| C4—C3—Br | 120.5 (5) | H8A—C8—H8B | 109.5 |
| C2—C3—Br | 119.1 (5) | O2—C8—H8C | 109.5 |
| C5—C4—C3 | 117.9 (6) | H8A—C8—H8C | 109.5 |
| C5—C4—H4A | 121.0 | H8B—C8—H8C | 109.5 |
| C6—N—C2—C3 | 1.8 (10) | C2—N—C6—C7 | 177.4 (6) |
| C6—N—C2—C1 | 178.4 (6) | C4—C5—C6—N | 0.4 (11) |
| N—C2—C3—C4 | −2.7 (11) | C4—C5—C6—C7 | −177.5 (7) |
| C1—C2—C3—C4 | −179.0 (6) | C8—O2—C7—O1 | −2.1 (11) |
| N—C2—C3—Br | 179.6 (5) | C8—O2—C7—C6 | 175.0 (6) |
| C1—C2—C3—Br | 3.3 (9) | N—C6—C7—O1 | −167.1 (7) |
| C2—C3—C4—C5 | 2.3 (11) | C5—C6—C7—O1 | 11.0 (11) |
| Br—C3—C4—C5 | 180.0 (5) | N—C6—C7—O2 | 15.6 (9) |
| C3—C4—C5—C6 | −1.2 (11) | C5—C6—C7—O2 | −166.3 (7) |
| C2—N—C6—C5 | −0.6 (10) |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2. |
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Oila, M. J., Tois, J. E. & Koskinen, A. M. P. (2005). Tetrahedron, 61, 10748–10756.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
The title compound is one of important intermediates for construction of novel supported PyOX-ligands (Oila et al., 2005). Here we report the crystal structure of the title compound, methyl 5-bromo-6-methylpicolinate (Fig. 1).
In the title compound, the bond lengths and angles are within normal ranges (Allen et al., 1987). The crystal structure is stabilized by a weak Br···Bri interaction at 3.715 (1) Å (Fig. 2; symmetry code as in Fig. 2).