Acta Cryst. (2009). E65, o2064 [ doi:10.1107/S1600536809030001 ]
Colourless crystals of the title compound, C10H12Br2O2, were synthesized from 1,2-dimethoxybenzene. The crystal structure is stabilized by intermolecular C-H
O hydrogen bonds.
Thirty-three percent HBr in AcOH (31.0 ml) was added to a solution of 1,2-dimethoxybenzene (10 g, 0.0725 mmol) and paraformaldehyde (4.35 g, 0.145 mmol) in acetic acid (100 ml), while the temperature was kept at 283 K. After stirring at room temperature for 20 h, the mixture was heated to 338 K for 1 h. The mixture was concentrated. EtOAc was added to get a white precipitate. The precipitate was filtered and washed with EtOAc to afford the title compound (9.72 g, 41.4%) as a white solid. Colourless crystals were obtained by vapor diffusion of pentane into a dichloromethane solution over a period of 3 days. 1H NMR (400 MHz, CDCl3, 295 K): 6.84 (2H, s), 4.63 (4H, s), 3.90 (6H, s).
All H atoms were placed in calculated positions and refined as riding, with C—H = 0.96–0.98 Å, and Uiso(H) = 1.2–1.5 Ueq(C).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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]](./jh2086fig1thm.gif)
| Fig. 1. The molecular structure with atom labels and 30% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./jh2086fig2thm.gif)
| Fig. 2. The packing diagram of molecular, viewed down the a axis, with the C—H···O interactions shown as dashed lines. |
| C10H12Br2O2 | F(000) = 1264 |
| Mr = 324.00 | Dx = 1.772 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 2795 reflections |
| a = 8.125 (6) Å | θ = 2.8–22.0° |
| b = 14.689 (10) Å | µ = 6.65 mm−1 |
| c = 20.353 (13) Å | T = 153 K |
| V = 2429 (3) Å3 | Prism, colourless |
| Z = 8 | 0.15 × 0.10 × 0.10 mm |
| Bruker APEXII CCD area-detector diffractometer | 2475 independent reflections |
| Radiation source: fine-focus sealed tube | 1643 reflections with I > 2σ(I) |
| graphite | Rint = 0.043 |
| φ and ω scans | θmax = 26.4°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −10→6 |
| Tmin = 0.456, Tmax = 0.516 | k = −18→17 |
| 12237 measured reflections | l = −25→20 |
| 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.117 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0542P)2 + 2.9265P] where P = (Fo2 + 2Fc2)/3 |
| 2475 reflections | (Δ/σ)max < 0.001 |
| 129 parameters | Δρmax = 0.89 e Å−3 |
| 0 restraints | Δρmin = −0.72 e Å−3 |
| C10H12Br2O2 | V = 2429 (3) Å3 |
| Mr = 324.00 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 8.125 (6) Å | µ = 6.65 mm−1 |
| b = 14.689 (10) Å | T = 153 K |
| c = 20.353 (13) Å | 0.15 × 0.10 × 0.10 mm |
| Bruker APEXII CCD area-detector diffractometer | 2475 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1643 reflections with I > 2σ(I) |
| Tmin = 0.456, Tmax = 0.516 | Rint = 0.043 |
| 12237 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.117 | Δρmax = 0.89 e Å−3 |
| S = 1.01 | Δρmin = −0.72 e Å−3 |
| 2475 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 | 0.41088 (8) | 0.58977 (4) | 0.08751 (3) | 0.0691 (2) | |
| Br2 | −0.16982 (8) | 0.43548 (4) | 0.13229 (3) | 0.0720 (2) | |
| C1 | 0.3186 (6) | 0.2549 (3) | 0.1807 (2) | 0.0410 (10) | |
| O2 | 0.3599 (4) | 0.1778 (2) | 0.21493 (15) | 0.0514 (8) | |
| C2 | 0.4121 (6) | 0.2681 (3) | 0.12203 (19) | 0.0385 (10) | |
| C3 | 0.1717 (6) | 0.3963 (3) | 0.1603 (2) | 0.0443 (10) | |
| O1 | 0.5203 (4) | 0.1999 (2) | 0.10678 (14) | 0.0549 (9) | |
| C4 | 0.2023 (6) | 0.3175 (3) | 0.1981 (2) | 0.0438 (10) | |
| H4 | 0.1399 | 0.3077 | 0.2370 | 0.053* | |
| C5 | 0.3861 (6) | 0.3470 (3) | 0.0855 (2) | 0.0428 (10) | |
| H5 | 0.4500 | 0.3574 | 0.0471 | 0.051* | |
| C8 | 0.0391 (7) | 0.4600 (3) | 0.1814 (2) | 0.0568 (13) | |
| H8A | 0.0745 | 0.5235 | 0.1733 | 0.068* | |
| H8B | 0.0194 | 0.4529 | 0.2291 | 0.068* | |
| C7 | 0.2466 (7) | 0.4960 (3) | 0.0628 (2) | 0.0554 (12) | |
| H7A | 0.1343 | 0.5206 | 0.0689 | 0.067* | |
| H7B | 0.2602 | 0.4801 | 0.0158 | 0.067* | |
| C6 | 0.2675 (6) | 0.4116 (3) | 0.1043 (2) | 0.0441 (11) | |
| C10 | 0.2760 (7) | 0.1627 (4) | 0.2764 (3) | 0.0681 (16) | |
| H10A | 0.2901 | 0.2159 | 0.3048 | 0.102* | |
| H10B | 0.3222 | 0.1088 | 0.2980 | 0.102* | |
| H10C | 0.1585 | 0.1529 | 0.2680 | 0.102* | |
| C20 | 0.6114 (8) | 0.2081 (4) | 0.0474 (3) | 0.0712 (16) | |
| H20A | 0.5362 | 0.2043 | 0.0098 | 0.107* | |
| H20B | 0.6923 | 0.1588 | 0.0447 | 0.107* | |
| H20C | 0.6684 | 0.2669 | 0.0467 | 0.107* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0821 (5) | 0.0486 (3) | 0.0765 (4) | −0.0146 (3) | 0.0161 (3) | 0.0010 (2) |
| Br2 | 0.0562 (4) | 0.0688 (4) | 0.0911 (5) | 0.0108 (3) | −0.0137 (3) | −0.0024 (3) |
| C1 | 0.048 (3) | 0.035 (2) | 0.040 (2) | 0.002 (2) | −0.0024 (19) | 0.0038 (18) |
| O2 | 0.051 (2) | 0.0500 (18) | 0.0532 (18) | 0.0134 (15) | 0.0079 (15) | 0.0175 (14) |
| C2 | 0.034 (2) | 0.040 (2) | 0.042 (2) | 0.0025 (19) | −0.0016 (19) | −0.0022 (18) |
| C3 | 0.046 (3) | 0.036 (2) | 0.051 (3) | 0.002 (2) | −0.008 (2) | −0.0076 (19) |
| O1 | 0.062 (2) | 0.0549 (19) | 0.0474 (17) | 0.0175 (18) | 0.0145 (16) | 0.0053 (15) |
| C4 | 0.050 (3) | 0.043 (2) | 0.039 (2) | 0.001 (2) | 0.000 (2) | −0.0005 (18) |
| C5 | 0.042 (3) | 0.048 (2) | 0.038 (2) | −0.003 (2) | −0.003 (2) | 0.0009 (19) |
| C8 | 0.063 (3) | 0.041 (3) | 0.067 (3) | 0.008 (2) | −0.008 (3) | −0.010 (2) |
| C7 | 0.058 (3) | 0.045 (3) | 0.063 (3) | −0.003 (2) | −0.013 (3) | 0.011 (2) |
| C6 | 0.052 (3) | 0.034 (2) | 0.046 (2) | −0.003 (2) | −0.006 (2) | 0.0016 (19) |
| C10 | 0.062 (4) | 0.075 (3) | 0.068 (3) | 0.013 (3) | 0.018 (3) | 0.031 (3) |
| C20 | 0.077 (4) | 0.075 (4) | 0.062 (3) | 0.019 (3) | 0.029 (3) | −0.006 (3) |
| Br1—C7 | 1.983 (5) | C5—C6 | 1.405 (6) |
| Br2—C8 | 2.002 (5) | C5—H5 | 0.9500 |
| C1—C4 | 1.365 (6) | C8—H8A | 0.9900 |
| C1—O2 | 1.372 (5) | C8—H8B | 0.9900 |
| C1—C2 | 1.428 (6) | C7—C6 | 1.510 (6) |
| O2—C10 | 1.442 (6) | C7—H7A | 0.9900 |
| C2—O1 | 1.368 (5) | C7—H7B | 0.9900 |
| C2—C5 | 1.394 (6) | C10—H10A | 0.9800 |
| C3—C6 | 1.399 (6) | C10—H10B | 0.9800 |
| C3—C4 | 1.413 (6) | C10—H10C | 0.9800 |
| C3—C8 | 1.490 (7) | C20—H20A | 0.9800 |
| O1—C20 | 1.422 (6) | C20—H20B | 0.9800 |
| C4—H4 | 0.9500 | C20—H20C | 0.9800 |
| C4—C1—O2 | 126.4 (4) | H8A—C8—H8B | 108.1 |
| C4—C1—C2 | 119.7 (4) | C6—C7—Br1 | 110.6 (3) |
| O2—C1—C2 | 114.0 (4) | C6—C7—H7A | 109.5 |
| C1—O2—C10 | 116.9 (4) | Br1—C7—H7A | 109.5 |
| O1—C2—C5 | 125.8 (4) | C6—C7—H7B | 109.5 |
| O1—C2—C1 | 115.7 (3) | Br1—C7—H7B | 109.5 |
| C5—C2—C1 | 118.5 (4) | H7A—C7—H7B | 108.1 |
| C6—C3—C4 | 118.5 (4) | C3—C6—C5 | 119.7 (4) |
| C6—C3—C8 | 122.5 (4) | C3—C6—C7 | 121.7 (4) |
| C4—C3—C8 | 119.0 (4) | C5—C6—C7 | 118.7 (4) |
| C2—O1—C20 | 117.7 (4) | O2—C10—H10A | 109.5 |
| C1—C4—C3 | 122.1 (4) | O2—C10—H10B | 109.5 |
| C1—C4—H4 | 118.9 | H10A—C10—H10B | 109.5 |
| C3—C4—H4 | 118.9 | O2—C10—H10C | 109.5 |
| C2—C5—C6 | 121.4 (4) | H10A—C10—H10C | 109.5 |
| C2—C5—H5 | 119.3 | H10B—C10—H10C | 109.5 |
| C6—C5—H5 | 119.3 | O1—C20—H20A | 109.5 |
| C3—C8—Br2 | 110.9 (3) | O1—C20—H20B | 109.5 |
| C3—C8—H8A | 109.5 | H20A—C20—H20B | 109.5 |
| Br2—C8—H8A | 109.5 | O1—C20—H20C | 109.5 |
| C3—C8—H8B | 109.5 | H20A—C20—H20C | 109.5 |
| Br2—C8—H8B | 109.5 | H20B—C20—H20C | 109.5 |
| C4—C1—O2—C10 | −2.0 (7) | O1—C2—C5—C6 | 177.7 (4) |
| C2—C1—O2—C10 | 177.1 (4) | C1—C2—C5—C6 | −2.0 (6) |
| C4—C1—C2—O1 | −177.0 (4) | C6—C3—C8—Br2 | 82.9 (5) |
| O2—C1—C2—O1 | 3.8 (6) | C4—C3—C8—Br2 | −97.1 (4) |
| C4—C1—C2—C5 | 2.7 (6) | C4—C3—C6—C5 | 2.6 (6) |
| O2—C1—C2—C5 | −176.5 (4) | C8—C3—C6—C5 | −177.4 (4) |
| C5—C2—O1—C20 | −2.2 (7) | C4—C3—C6—C7 | −177.6 (4) |
| C1—C2—O1—C20 | 177.5 (4) | C8—C3—C6—C7 | 2.3 (7) |
| O2—C1—C4—C3 | 178.3 (4) | C2—C5—C6—C3 | −0.7 (7) |
| C2—C1—C4—C3 | −0.8 (7) | C2—C5—C6—C7 | 179.6 (4) |
| C6—C3—C4—C1 | −1.9 (7) | Br1—C7—C6—C3 | 96.8 (5) |
| C8—C3—C4—C1 | 178.1 (4) | Br1—C7—C6—C5 | −83.5 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C8—H8A···O2i | 0.99 | 2.48 | 3.373 (6) | 150 |
| C10—H10C···O2ii | 0.98 | 2.48 | 3.392 (7) | 155 |
| Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, y, −z+1/2. |
| Br1—C7 | 1.983 (5) | C2—C5 | 1.394 (6) |
| Br2—C8 | 2.002 (5) | C3—C6 | 1.399 (6) |
| C1—C4 | 1.365 (6) | C3—C4 | 1.413 (6) |
| C1—O2 | 1.372 (5) | C3—C8 | 1.490 (7) |
| C1—C2 | 1.428 (6) | O1—C20 | 1.422 (6) |
| O2—C10 | 1.442 (6) | C5—C6 | 1.405 (6) |
| C2—O1 | 1.368 (5) | C7—C6 | 1.510 (6) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C8—H8A···O2i | 0.99 | 2.48 | 3.373 (6) | 150 |
| C10—H10C···O2ii | 0.98 | 2.48 | 3.392 (7) | 155 |
| Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, y, −z+1/2. |
The author is grateful to the Sciences Foundation of Shandong Provincial Education Department (No. J06D61) as well as the Doctoral Science Foundation of Zaozhuang University.
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Bis-bromomethylation of 1,2-dimethoxybenzene afforded the title compound(I), which was useful for the preparation of crown ether derivatives and isoindoline compounds (Diederich et al., 1993; Walpole et al., 1994; Dalence-Guzman et al., 2008). It had been believed difficult to introduce hydroxyl groups directly to the 5- and 6-positions of isoindoline. With I as an intermediate, novel isoindoline derivatives could be easily prepared. The crystal structure of I is stabilized by intermolecular C–H···O hydrogen bonds.