Acta Cryst. (2008). E64, o1064 [ doi:10.1107/S1600536808013767 ]
In the molecule of the title compound, C11H12BrNO2, a weak intramolecular C-H
Br hydrogen bond results in the formation of a five-membered ring, which adopts an envelope conformation with the H atom displaced by 0.486 Å from the plane of the other ring atoms. In the crystal structure, intermolecular C-HO hydrogen bonds link the molecules.
For the preparation of the title compound, beta-(2-bromo-4,5-dimethoxypenyl) -alpha-cyanoproponic acid (16 mmol) was dissolved in dimethylacetamide (10 ml), the mixture was heated at 443 K and evolution of the calculated amount of CO2 ceased after 30 min. The mixture was poured into water and set aside overnight. Crystals were separated, collected and washed with water and hexane. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.
H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hk2461fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond is shown as dashed line. |
![[Figure 2]](./hk2461fig2thm.gif)
| Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines. |
| C11H12BrNO2 | Z = 8 |
| Mr = 270.13 | F000 = 1088 |
| Tetragonal, P42bc | Dx = 1.556 Mg m−3 |
| Hall symbol: P 4c -2ab | Mo Kα radiation λ = 0.71073 Å |
| a = 17.552 (3) Å | Cell parameters from 25 reflections |
| b = 17.552 (3) Å | θ = 10–13º |
| c = 7.4870 (15) Å | µ = 3.54 mm−1 |
| α = 90º | T = 294 (2) K |
| β = 90º | Block, colorless |
| γ = 90º | 0.30 × 0.10 × 0.10 mm |
| V = 2306.5 (7) Å3 |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.047 |
| Radiation source: fine-focus sealed tube | θmax = 25.2º |
| Monochromator: graphite | θmin = 1.6º |
| T = 294(2) K | h = −21→21 |
| ω/2θ scans | k = −21→0 |
| Absorption correction: ψ scan (North et al., 1968) | l = 0→8 |
| Tmin = 0.416, Tmax = 0.718 | 3 standard reflections |
| 4281 measured reflections | every 120 min |
| 1128 independent reflections | intensity decay: none |
| 657 reflections with I > 2σ(I) |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.052 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.113 | Δρmax = 0.36 e Å−3 |
| S = 0.99 | Δρmin = −0.39 e Å−3 |
| 1128 reflections | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 137 parameters | Extinction coefficient: 0.0026 (5) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with no Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: 0.00 (3) |
| Hydrogen site location: inferred from neighbouring sites |
| C11H12BrNO2 | γ = 90º |
| Mr = 270.13 | V = 2306.5 (7) Å3 |
| Tetragonal, P42bc | Z = 8 |
| a = 17.552 (3) Å | Mo Kα |
| b = 17.552 (3) Å | µ = 3.54 mm−1 |
| c = 7.4870 (15) Å | T = 294 (2) K |
| α = 90º | 0.30 × 0.10 × 0.10 mm |
| β = 90º |
| Enraf–Nonius CAD-4 diffractometer | 657 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.047 |
| Tmin = 0.416, Tmax = 0.718 | 3 standard reflections |
| 4281 measured reflections | every 120 min |
| 1128 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
| wR(F2) = 0.113 | Δρmax = 0.36 e Å−3 |
| S = 0.99 | Δρmin = −0.39 e Å−3 |
| 1128 reflections | Absolute structure: Flack (1983), with no Friedel pairs |
| 137 parameters | Flack parameter: 0.00 (3) |
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 > 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 | 0.95483 (5) | 0.91044 (5) | 0.9098 (3) | 0.0796 (5) | |
| N | 0.6404 (5) | 0.9114 (5) | 0.6468 (17) | 0.083 (4) | |
| O1 | 0.7337 (3) | 0.6500 (3) | 0.8860 (13) | 0.051 (2) | |
| O2 | 0.8737 (4) | 0.6253 (3) | 0.8147 (10) | 0.055 (2) | |
| C1 | 0.6900 (6) | 0.9379 (5) | 0.7195 (18) | 0.057 (3) | |
| C2 | 0.7527 (6) | 0.9707 (5) | 0.8211 (15) | 0.060 (4) | |
| H2A | 0.7383 | 1.0216 | 0.8585 | 0.073* | |
| H2B | 0.7965 | 0.9754 | 0.7429 | 0.073* | |
| C3 | 0.7763 (5) | 0.9255 (5) | 0.9855 (13) | 0.050 (3) | |
| H3A | 0.7329 | 0.9212 | 1.0649 | 0.060* | |
| H3B | 0.8158 | 0.9535 | 1.0482 | 0.060* | |
| C4 | 0.8058 (4) | 0.8459 (4) | 0.9433 (19) | 0.040 (3) | |
| C5 | 0.8811 (4) | 0.8304 (4) | 0.906 (2) | 0.043 (2) | |
| C6 | 0.9068 (5) | 0.7583 (5) | 0.8663 (14) | 0.053 (5) | |
| H6A | 0.9585 | 0.7501 | 0.8462 | 0.064* | |
| C7 | 0.8568 (5) | 0.6988 (4) | 0.8560 (11) | 0.034 (3) | |
| C8 | 0.7797 (4) | 0.7129 (4) | 0.899 (2) | 0.038 (2) | |
| C9 | 0.7556 (4) | 0.7846 (4) | 0.939 (2) | 0.040 (3) | |
| H9A | 0.7043 | 0.7929 | 0.9639 | 0.047* | |
| C10 | 0.6556 (4) | 0.6598 (4) | 0.932 (3) | 0.056 (3) | |
| H10A | 0.6297 | 0.6117 | 0.9225 | 0.084* | |
| H10B | 0.6326 | 0.6957 | 0.8516 | 0.084* | |
| H10C | 0.6519 | 0.6784 | 1.0520 | 0.084* | |
| C11 | 0.9502 (5) | 0.6090 (5) | 0.758 (2) | 0.077 (4) | |
| H11A | 0.9549 | 0.5556 | 0.7324 | 0.116* | |
| H11B | 0.9852 | 0.6228 | 0.8507 | 0.116* | |
| H11C | 0.9615 | 0.6378 | 0.6519 | 0.116* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br | 0.0517 (6) | 0.0477 (6) | 0.1394 (12) | −0.0149 (4) | −0.0013 (13) | −0.0086 (14) |
| N | 0.084 (7) | 0.070 (6) | 0.095 (10) | 0.022 (5) | −0.025 (8) | −0.018 (7) |
| O1 | 0.039 (3) | 0.036 (3) | 0.078 (7) | −0.003 (2) | 0.006 (5) | −0.015 (5) |
| O2 | 0.044 (4) | 0.031 (4) | 0.090 (6) | 0.010 (3) | 0.009 (4) | 0.000 (4) |
| C1 | 0.067 (8) | 0.041 (6) | 0.062 (10) | 0.013 (6) | 0.002 (7) | −0.009 (6) |
| C2 | 0.064 (7) | 0.032 (6) | 0.085 (10) | 0.008 (5) | −0.007 (7) | −0.010 (6) |
| C3 | 0.042 (6) | 0.055 (6) | 0.052 (9) | 0.002 (5) | 0.009 (5) | −0.012 (6) |
| C4 | 0.041 (5) | 0.035 (4) | 0.045 (8) | −0.001 (3) | −0.002 (7) | −0.006 (7) |
| C5 | 0.042 (5) | 0.038 (5) | 0.047 (7) | −0.011 (4) | −0.006 (9) | −0.007 (9) |
| C6 | 0.033 (4) | 0.042 (5) | 0.085 (14) | 0.001 (4) | 0.003 (6) | −0.003 (6) |
| C7 | 0.041 (5) | 0.031 (4) | 0.030 (8) | 0.005 (4) | −0.008 (4) | −0.002 (4) |
| C8 | 0.039 (4) | 0.026 (4) | 0.048 (7) | −0.007 (3) | 0.013 (8) | −0.001 (7) |
| C9 | 0.037 (4) | 0.038 (4) | 0.044 (7) | 0.001 (4) | −0.005 (7) | 0.002 (7) |
| C10 | 0.036 (5) | 0.053 (5) | 0.079 (8) | −0.013 (4) | 0.001 (9) | 0.008 (10) |
| C11 | 0.054 (6) | 0.049 (6) | 0.128 (13) | 0.009 (5) | 0.000 (8) | −0.013 (8) |
| Br—C5 | 1.911 (7) | C4—C9 | 1.391 (10) |
| N—C1 | 1.128 (13) | C5—C6 | 1.376 (11) |
| O1—C8 | 1.371 (9) | C6—C7 | 1.367 (11) |
| O1—C10 | 1.422 (9) | C6—H6A | 0.9300 |
| O2—C7 | 1.358 (9) | C7—C8 | 1.414 (10) |
| O2—C11 | 1.438 (10) | C8—C9 | 1.360 (10) |
| C1—C2 | 1.456 (14) | C9—H9A | 0.9300 |
| C2—C3 | 1.521 (13) | C10—H10A | 0.9600 |
| C2—H2A | 0.9700 | C10—H10B | 0.9600 |
| C2—H2B | 0.9700 | C10—H10C | 0.9600 |
| C3—C4 | 1.524 (11) | C11—H11A | 0.9600 |
| C3—H3A | 0.9700 | C11—H11B | 0.9600 |
| C3—H3B | 0.9700 | C11—H11C | 0.9600 |
| C4—C5 | 1.376 (11) | ||
| C8—O1—C10 | 116.9 (6) | C5—C6—H6A | 119.9 |
| C7—O2—C11 | 117.4 (7) | O2—C7—C6 | 126.7 (8) |
| N—C1—C2 | 177.3 (14) | O2—C7—C8 | 115.3 (7) |
| C1—C2—C3 | 115.0 (9) | C6—C7—C8 | 117.9 (8) |
| C1—C2—H2A | 108.5 | C9—C8—O1 | 125.3 (7) |
| C3—C2—H2A | 108.5 | C9—C8—C7 | 120.7 (7) |
| C1—C2—H2B | 108.5 | O1—C8—C7 | 113.9 (7) |
| C3—C2—H2B | 108.5 | C8—C9—C4 | 121.5 (8) |
| H2A—C2—H2B | 107.5 | C8—C9—H9A | 119.2 |
| C2—C3—C4 | 113.7 (8) | C4—C9—H9A | 119.2 |
| C2—C3—H3A | 108.8 | O1—C10—H10A | 109.5 |
| C4—C3—H3A | 108.8 | O1—C10—H10B | 109.5 |
| C2—C3—H3B | 108.8 | H10A—C10—H10B | 109.5 |
| C4—C3—H3B | 108.8 | O1—C10—H10C | 109.5 |
| H3A—C3—H3B | 107.7 | H10A—C10—H10C | 109.5 |
| C5—C4—C9 | 116.8 (7) | H10B—C10—H10C | 109.5 |
| C5—C4—C3 | 123.3 (7) | O2—C11—H11A | 109.5 |
| C9—C4—C3 | 119.9 (8) | O2—C11—H11B | 109.5 |
| C4—C5—C6 | 122.7 (7) | H11A—C11—H11B | 109.5 |
| C4—C5—Br | 120.1 (6) | O2—C11—H11C | 109.5 |
| C6—C5—Br | 117.1 (6) | H11A—C11—H11C | 109.5 |
| C7—C6—C5 | 120.2 (8) | H11B—C11—H11C | 109.5 |
| C7—C6—H6A | 119.9 | ||
| C1—C2—C3—C4 | 62.4 (12) | C5—C6—C7—C8 | −4.2 (18) |
| C2—C3—C4—C5 | 88.6 (16) | C10—O1—C8—C9 | −6(3) |
| C2—C3—C4—C9 | −90.8 (16) | C10—O1—C8—C7 | 178.6 (13) |
| C9—C4—C5—C6 | 0(2) | O2—C7—C8—C9 | −178.5 (13) |
| C3—C4—C5—C6 | −179.2 (13) | C6—C7—C8—C9 | 4(2) |
| C9—C4—C5—Br | −179.7 (11) | O2—C7—C8—O1 | −2.4 (17) |
| C3—C4—C5—Br | 1(2) | C6—C7—C8—O1 | −179.8 (11) |
| C4—C5—C6—C7 | 2(2) | O1—C8—C9—C4 | −177.5 (13) |
| Br—C5—C6—C7 | −177.9 (9) | C7—C8—C9—C4 | −2(3) |
| C11—O2—C7—C6 | −7.0 (15) | C5—C4—C9—C8 | 0(3) |
| C11—O2—C7—C8 | 175.9 (12) | C3—C4—C9—C8 | 179.1 (13) |
| C5—C6—C7—O2 | 178.7 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···O1i | 0.97 | 2.32 | 3.193 (10) | 150 |
| C3—H3B···Br | 0.97 | 2.76 | 3.195 (9) | 108 |
| Symmetry codes: (i) −x+3/2, y+1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···O1i | 0.97 | 2.32 | 3.193 (10) | 150 |
| C3—H3B···Br | 0.97 | 2.76 | 3.195 (9) | 108 |
| Symmetry codes: (i) −x+3/2, y+1/2, z. |
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2-Bromo-4,5-dimethoxyhydrocinnamonitrile is the precursor of 1-cyano-4,5-di- methoxybenzocyclobutene, which is a key intermediate of ivabradine (Lerestif et al., 2005), xylopinine (Kametani et al., 1973) and 4-substituted 3a,4,5,9 b-terahydrobenz[e]isoindolinea (Paull & Cheng, 1972). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound, (I).
In the molecule of (I), (Fig. 1), ring A (C4-C9) is, of course, planar. Br, O1, O2, C3 and C10 atoms lie in the ring plane. A weak intramolecular C-H···Br [C3-H3B = 0.97, H3B···Br = 2.76, C3···Br = 3.195 (9) Å and C3-H3B···Br = 108°] hydrogen bond results in the formation of a five-membered ring B (C3-C5/Br/H3B), which adopts envelope conformation with hydrogen atom displaced by -0.486 (3) Å from the plane of the other ring atoms.
In the crystal structure, intermolecular C-H···O [C2-H2A = 0.97, H2A···O1 = 2.32, C2···O1 = 3.193 (8) Å and C2-H2A···O1 = 150°] hydrogen bonds link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.