Acta Cryst. (2011). E67, o794 [ doi:10.1107/S1600536811007434 ]
In the title compound, C10H7Br2NO, the molecule possesses a planar geometry with an r.m.s deviation of 0.0383 Å for all non-H atoms. The crystal structure displays O-H
N and C-HO hydrogen bonding, as well as BrBr contacts [3.6284 (4) Å].
As described by Choi & Chi (2004), 5 ml of bromine in MeOH (50 ml) was added to a mixture of 8-hydroxy-2-methylquinoline (5.0 g, 31.4 mmol), NaHCO3 (5 g) and MeOH (50 ml). After stirring for 5 min at room temperature, Na2SO3 (2.5 g) was added, and then the mixture was filtered and washed with H2O (100 ml). The white solid was dried in vacuo to give the title compound as raw product (8.9 g, 89%). Recrystallization from boiling and slowly cooling to room temperature ethanol yielded single crystals suitable for X-ray crystallography.
H atoms were positioned geometrically and allowed to ride on their parent atoms, with O—H = 0.84 Å, C—H = 0.95–0.98 Å and Uiso(H) = 1.2–1.5 Ueq(parent atom).
Data collection: SMART (Bruker, 2007); cell refinement: 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./im2267fig1thm.gif)
| Fig. 1. Perspective view of (I), showing 50% probability displacementellipsoids for the non-H atoms. |
![[Figure 2]](./im2267fig2thm.gif)
| Fig. 2. View of the crystal packing of the title compound along the crystallographic b axis. C–H···O, O–H···N and Br···Br contacts are shown as broken lines. |
| C10H7Br2NO | F(000) = 1216 |
| Mr = 316.99 | Dx = 2.205 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 9610 reflections |
| a = 22.2221 (5) Å | θ = 2.4–29.2° |
| b = 4.0479 (1) Å | µ = 8.45 mm−1 |
| c = 21.7221 (4) Å | T = 93 K |
| β = 102.167 (1)° | Piece, colourless |
| V = 1910.07 (7) Å3 | 0.40 × 0.24 × 0.22 mm |
| Z = 8 |
| Bruker SMART CCD area-detector diffractometer | 1727 independent reflections |
| Radiation source: fine-focus sealed tube | 1629 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| φ and ω scans | θmax = 25.2°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −26→25 |
| Tmin = 0.133, Tmax = 0.258 | k = −4→4 |
| 13437 measured reflections | l = −26→26 |
| 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)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.046 | H-atom parameters constrained |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0262P)2 + 2.9807P] where P = (Fo2 + 2Fc2)/3 |
| 1727 reflections | (Δ/σ)max = 0.001 |
| 129 parameters | Δρmax = 0.36 e Å−3 |
| 0 restraints | Δρmin = −0.60 e Å−3 |
| C10H7Br2NO | V = 1910.07 (7) Å3 |
| Mr = 316.99 | Z = 8 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 22.2221 (5) Å | µ = 8.45 mm−1 |
| b = 4.0479 (1) Å | T = 93 K |
| c = 21.7221 (4) Å | 0.40 × 0.24 × 0.22 mm |
| β = 102.167 (1)° |
| Bruker SMART CCD area-detector diffractometer | 1727 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | 1629 reflections with I > 2σ(I) |
| Tmin = 0.133, Tmax = 0.258 | Rint = 0.025 |
| 13437 measured reflections | θmax = 25.2° |
| R[F2 > 2σ(F2)] = 0.017 | H-atom parameters constrained |
| wR(F2) = 0.046 | Δρmax = 0.36 e Å−3 |
| S = 1.11 | Δρmin = −0.60 e Å−3 |
| 1727 reflections | Absolute structure: ? |
| 129 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 | ||
| Br1 | 0.226304 (10) | 0.34054 (6) | 0.083369 (10) | 0.02104 (8) | |
| Br2 | 0.431764 (10) | 1.01225 (5) | 0.033388 (9) | 0.02065 (8) | |
| N1 | 0.42288 (8) | 0.6326 (4) | 0.26148 (8) | 0.0151 (4) | |
| O1 | 0.47717 (7) | 0.9601 (4) | 0.17443 (7) | 0.0197 (3) | |
| H1 | 0.5012 | 0.8441 | 0.2009 | 0.030* | |
| C1 | 0.39566 (10) | 0.4874 (5) | 0.30307 (10) | 0.0168 (4) | |
| C2 | 0.33816 (10) | 0.3287 (5) | 0.28492 (10) | 0.0198 (5) | |
| H2 | 0.3204 | 0.2213 | 0.3157 | 0.024* | |
| C3 | 0.30807 (10) | 0.3291 (5) | 0.22338 (10) | 0.0186 (5) | |
| H3 | 0.2693 | 0.2223 | 0.2111 | 0.022* | |
| C4 | 0.33477 (10) | 0.4888 (5) | 0.17805 (10) | 0.0144 (4) | |
| C5 | 0.30664 (10) | 0.5140 (5) | 0.11344 (10) | 0.0155 (4) | |
| C6 | 0.33502 (10) | 0.6709 (5) | 0.07179 (10) | 0.0174 (4) | |
| H6 | 0.3154 | 0.6859 | 0.0286 | 0.021* | |
| C7 | 0.39324 (10) | 0.8094 (5) | 0.09334 (10) | 0.0150 (4) | |
| C8 | 0.42345 (10) | 0.8007 (5) | 0.15583 (10) | 0.0145 (4) | |
| C9 | 0.39347 (10) | 0.6360 (5) | 0.19921 (9) | 0.0137 (4) | |
| C10 | 0.42720 (11) | 0.4996 (6) | 0.37143 (10) | 0.0224 (5) | |
| H10A | 0.4668 | 0.3840 | 0.3774 | 0.034* | |
| H10B | 0.4012 | 0.3923 | 0.3968 | 0.034* | |
| H10C | 0.4342 | 0.7303 | 0.3847 | 0.034* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.01485 (13) | 0.02683 (14) | 0.02053 (13) | −0.00403 (8) | 0.00170 (9) | −0.00389 (8) |
| Br2 | 0.02015 (14) | 0.02857 (14) | 0.01417 (13) | −0.00252 (9) | 0.00577 (9) | 0.00366 (8) |
| N1 | 0.0131 (9) | 0.0189 (9) | 0.0133 (8) | 0.0042 (7) | 0.0024 (7) | 0.0016 (7) |
| O1 | 0.0130 (8) | 0.0279 (9) | 0.0169 (8) | −0.0037 (6) | 0.0001 (6) | 0.0048 (6) |
| C1 | 0.0168 (11) | 0.0181 (11) | 0.0160 (10) | 0.0068 (8) | 0.0048 (9) | 0.0025 (8) |
| C2 | 0.0196 (12) | 0.0220 (12) | 0.0198 (11) | 0.0029 (9) | 0.0088 (9) | 0.0040 (9) |
| C3 | 0.0142 (11) | 0.0193 (11) | 0.0233 (11) | 0.0004 (8) | 0.0063 (9) | 0.0011 (9) |
| C4 | 0.0124 (11) | 0.0144 (10) | 0.0172 (11) | 0.0037 (8) | 0.0045 (8) | −0.0007 (8) |
| C5 | 0.0114 (10) | 0.0159 (10) | 0.0187 (10) | 0.0005 (8) | 0.0021 (8) | −0.0027 (8) |
| C6 | 0.0174 (11) | 0.0210 (11) | 0.0133 (10) | 0.0041 (9) | 0.0022 (8) | −0.0015 (8) |
| C7 | 0.0157 (11) | 0.0168 (10) | 0.0143 (10) | 0.0023 (8) | 0.0071 (8) | 0.0017 (8) |
| C8 | 0.0113 (10) | 0.0153 (10) | 0.0174 (10) | 0.0032 (8) | 0.0039 (8) | 0.0003 (8) |
| C9 | 0.0131 (11) | 0.0152 (10) | 0.0130 (10) | 0.0043 (8) | 0.0030 (8) | −0.0011 (8) |
| C10 | 0.0236 (13) | 0.0286 (13) | 0.0152 (11) | 0.0026 (9) | 0.0047 (9) | 0.0035 (9) |
| Br1—C5 | 1.901 (2) | C3—H3 | 0.9500 |
| Br2—C7 | 1.890 (2) | C4—C5 | 1.415 (3) |
| N1—C1 | 1.326 (3) | C4—C9 | 1.420 (3) |
| N1—C9 | 1.373 (3) | C5—C6 | 1.364 (3) |
| O1—C8 | 1.342 (3) | C6—C7 | 1.397 (3) |
| O1—H1 | 0.8400 | C6—H6 | 0.9500 |
| C1—C2 | 1.410 (3) | C7—C8 | 1.382 (3) |
| C1—C10 | 1.503 (3) | C8—C9 | 1.429 (3) |
| C2—C3 | 1.363 (3) | C10—H10A | 0.9800 |
| C2—H2 | 0.9500 | C10—H10B | 0.9800 |
| C3—C4 | 1.409 (3) | C10—H10C | 0.9800 |
| C1—N1—C9 | 119.01 (18) | C5—C6—H6 | 120.3 |
| C8—O1—H1 | 109.5 | C7—C6—H6 | 120.3 |
| N1—C1—C2 | 121.88 (19) | C8—C7—C6 | 122.87 (19) |
| N1—C1—C10 | 118.3 (2) | C8—C7—Br2 | 119.40 (16) |
| C2—C1—C10 | 119.8 (2) | C6—C7—Br2 | 117.73 (15) |
| C3—C2—C1 | 120.1 (2) | O1—C8—C7 | 120.03 (19) |
| C3—C2—H2 | 119.9 | O1—C8—C9 | 122.33 (18) |
| C1—C2—H2 | 119.9 | C7—C8—C9 | 117.52 (19) |
| C2—C3—C4 | 119.6 (2) | N1—C9—C4 | 121.94 (19) |
| C2—C3—H3 | 120.2 | N1—C9—C8 | 117.59 (18) |
| C4—C3—H3 | 120.2 | C4—C9—C8 | 120.45 (18) |
| C3—C4—C5 | 124.3 (2) | C1—C10—H10A | 109.5 |
| C3—C4—C9 | 117.38 (19) | C1—C10—H10B | 109.5 |
| C5—C4—C9 | 118.34 (19) | H10A—C10—H10B | 109.5 |
| C6—C5—C4 | 121.5 (2) | C1—C10—H10C | 109.5 |
| C6—C5—Br1 | 118.43 (16) | H10A—C10—H10C | 109.5 |
| C4—C5—Br1 | 120.05 (16) | H10B—C10—H10C | 109.5 |
| C5—C6—C7 | 119.32 (19) | ||
| C9—N1—C1—C2 | 1.8 (3) | C6—C7—C8—O1 | −174.87 (19) |
| C9—N1—C1—C10 | −177.25 (18) | Br2—C7—C8—O1 | 5.8 (3) |
| N1—C1—C2—C3 | −1.8 (3) | C6—C7—C8—C9 | 1.2 (3) |
| C10—C1—C2—C3 | 177.2 (2) | Br2—C7—C8—C9 | −178.10 (15) |
| C1—C2—C3—C4 | 0.0 (3) | C1—N1—C9—C4 | 0.0 (3) |
| C2—C3—C4—C5 | −177.7 (2) | C1—N1—C9—C8 | 178.67 (18) |
| C2—C3—C4—C9 | 1.6 (3) | C3—C4—C9—N1 | −1.7 (3) |
| C3—C4—C5—C6 | −179.7 (2) | C5—C4—C9—N1 | 177.67 (18) |
| C9—C4—C5—C6 | 1.0 (3) | C3—C4—C9—C8 | 179.69 (19) |
| C3—C4—C5—Br1 | 2.5 (3) | C5—C4—C9—C8 | −1.0 (3) |
| C9—C4—C5—Br1 | −176.86 (14) | O1—C8—C9—N1 | −2.8 (3) |
| C4—C5—C6—C7 | 0.1 (3) | C7—C8—C9—N1 | −178.78 (18) |
| Br1—C5—C6—C7 | 177.96 (15) | O1—C8—C9—C4 | 175.90 (18) |
| C5—C6—C7—C8 | −1.3 (3) | C7—C8—C9—C4 | −0.1 (3) |
| C5—C6—C7—Br2 | 178.09 (16) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1i | 0.84 | 1.92 | 2.707 (2) | 157 |
| C10—H10A···O1ii | 0.98 | 2.52 | 3.342 (3) | 141 |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, y−1, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1i | 0.84 | 1.92 | 2.707 (2) | 157 |
| C10—H10A···O1ii | 0.98 | 2.52 | 3.342 (3) | 141 |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, y−1, −z+1/2. |
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The molecular shape of the title compound is best described by the planarity of the molecule (Fig. 1), expressed by the RMS deviation of all non-hydrogen fitted atoms being 0.0383 Å. Molecular dimers are formed by a conventional hydrogen bridge, O1—H1···N1 [d = 2.707 (2) Å, θ = 157°] (Fig. 2) that is also found in the structure of the parent 8-hydroxyquinoline (Banerjee & Saha, 1986). In addition, a C—H···O contact creates chains along the crystallographic b axis. Distances between adjacent aromatic planes of 4.1 Å indicate the absence of π stacking interactions. However, halogen interactions of type I mode (Awwadi et al. 2006) represented by the Br2···Br2 contact [d = 3.6284 (4) Å, θ1 = θ2 = 143.3°] connect the formed dimers. Considering analogous dimer formation in the parent 8-hydroxyquinoline, this particular halogen contact is largely attributable to crystal packing effects.