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access1-Bromo-2-[(E)-2-nitroethenyl]benzene
aResearch Center for Engineering Technology of Polymeric Composites of Shanxi Province, College of Materials Science and Engineering, North University of China, Taiyuan 030051, People's Republic of China, and bCollege of Chemsitry, Nankai University, Tianjin 300071, People's Republic of China
*Correspondence e-mail: zph2004@yahoo.com.cn
In the title compound, C8H6BrNO2, the dihedral angle between the planes of the benzene ring and the nitro group is 22.99 (12)°. In the crystal, inversion dimers associated by pairs of short Br⋯O contacts [3.2319 (17) Å] occur.
Related literature
For background to nitro-olefins and their synthetic applications, see: Barret & Graboski (1986![[Barret, A. G. M. & Graboski, G. G. (1986). Chem. Rev. 86, 751-762.]](../../../../../../logos/arrows/e_arr.gif "Barret, A. G. M. & Graboski, G. G. (1986). Chem. Rev. 86, 751-762.")
); Berner et al. (2002); Ballini et al. (1992).
![[Scheme 1]](hb6539scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear; data reduction: CrystalClear; 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: CrystalStructure (Rigaku/MSC, 2005).
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811050963/hb6539sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050963/hb6539Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811050963/hb6539Isup3.cml
2-Bromobenzaladehyde (39.8 mmol, 7.36 g), nitromethane (99.2 mmol, 5.38 ml), and methanol (16.80 ml) are added to a 3-neck round bottomed flask and cooled to zero degree centigrade. While maintaining the internal reaction temperature between zero and ten degrees centigrade, aqueous 1M NaOH (100.2 mmol, 100.20 ml) is added by an additon funnel and the mixture is stirred for 15 min. Ice water mixture (70.00 ml) is added and the reaction is stirred at zero degree centigrade for 30 min. The reaction mixture is slowly added to aqueous 8M HCl (536.0 mmol, 67.00 ml) and allowed to stir until the rection is confirmed complete by TLC. The reaction mixture is filtered and recrystallized from ethanol to give the product. Colourless prisms of (I) were obtained by slow evaporation of the dichloromethane/n-hexane solutions at room temperature.
All the H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
Nitro-olefins are useful building blocks in organic synthesis (Barret et al., 1986). Furthermore, the charater of these compounds as electron-deficient allows easy 1,4-addtion reactions and this opens the way to synthetically useful C—C and C—X (X = N, O) bond-forming reactions (Berner et al. (2002), Ballini et al. (1992)). The title compound, (I), belongs to the class of fuctionalized nitroolefins.
As shown in Fig. 1, the dihedral angle between carbon double bond and phenyl groups is 12.2 (2) °. As shown in Fig. 2, the crystal packing shows the weak O···Br intermolecular interactions.
For background to nitro-olefins and their synthetic applications, see: Barret & Graboski (1986); Berner et al. (2002); Ballini et al. (1992).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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: CrystalStructure (Rigaku/MSC, 2005).
![[Figure 1]](./hb6539fig1thm.gif) | Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. |
![[Figure 2]](./hb6539fig2thm.gif) | Fig. 2. The crystal packing for (I). |
| C8H6BrNO2 | F(000) = 448 |
| Mr = 228.05 | Dx = 1.856 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.9570 (18) Å | Cell parameters from 2970 reflections |
| b = 15.646 (2) Å | θ = 2.6–28.0° |
| c = 7.9470 (13) Å | µ = 4.99 mm−1 |
| β = 109.336 (5)° | T = 113 K |
| V = 816.2 (3) Å3 | Prism, colorless |
| Z = 4 | 0.20 × 0.18 × 0.16 mm |
| Rigaku Saturn724 CCD diffractometer | 1945 independent reflections |
| Radiation source: rotating anode | 1466 reflections with I > 2σ(I) |
| Multilayer monochromator | Rint = 0.042 |
| Detector resolution: 14.22 pixels mm-1 | θmax = 27.8°, θmin = 2.6° |
| ω and φ scans | h = −9→9 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −20→20 |
| Tmin = 0.435, Tmax = 0.502 | l = −10→10 |
| 10346 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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.056 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.020P)2] where P = (Fo2 + 2Fc2)/3 |
| 1945 reflections | (Δ/σ)max = 0.003 |
| 109 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.78 e Å−3 |
| C8H6BrNO2 | V = 816.2 (3) Å3 |
| Mr = 228.05 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.9570 (18) Å | µ = 4.99 mm−1 |
| b = 15.646 (2) Å | T = 113 K |
| c = 7.9470 (13) Å | 0.20 × 0.18 × 0.16 mm |
| β = 109.336 (5)° |
| Rigaku Saturn724 CCD diffractometer | 1945 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1466 reflections with I > 2σ(I) |
| Tmin = 0.435, Tmax = 0.502 | Rint = 0.042 |
| 10346 measured reflections |
| R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
| wR(F2) = 0.056 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.33 e Å−3 |
| 1945 reflections | Δρmin = −0.78 e Å−3 |
| 109 parameters |
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 | 0.39712 (4) | 0.607142 (14) | 0.81215 (3) | 0.02051 (8) | |
| O1 | 0.1113 (2) | 0.21839 (10) | 0.6270 (2) | 0.0218 (4) | |
| O2 | 0.3362 (2) | 0.29119 (10) | 0.8336 (2) | 0.0238 (4) | |
| N1 | 0.2150 (3) | 0.28344 (11) | 0.6807 (2) | 0.0153 (4) | |
| C1 | 0.3043 (3) | 0.58570 (14) | 0.5620 (3) | 0.0141 (5) | |
| C2 | 0.2914 (3) | 0.65593 (14) | 0.4508 (3) | 0.0153 (5) | |
| H2 | 0.3316 | 0.7109 | 0.5007 | 0.018* | |
| C3 | 0.2203 (3) | 0.64552 (14) | 0.2684 (3) | 0.0179 (5) | |
| H3 | 0.2093 | 0.6935 | 0.1925 | 0.021* | |
| C4 | 0.1644 (3) | 0.56451 (15) | 0.1954 (3) | 0.0190 (5) | |
| H4 | 0.1156 | 0.5571 | 0.0696 | 0.023* | |
| C5 | 0.1804 (3) | 0.49484 (14) | 0.3071 (3) | 0.0160 (5) | |
| H5 | 0.1438 | 0.4398 | 0.2561 | 0.019* | |
| C6 | 0.2490 (3) | 0.50341 (13) | 0.4930 (3) | 0.0119 (4) | |
| C7 | 0.2672 (3) | 0.42903 (13) | 0.6100 (3) | 0.0132 (5) | |
| H7 | 0.3405 | 0.4360 | 0.7334 | 0.016* | |
| C8 | 0.1882 (3) | 0.35266 (13) | 0.5549 (3) | 0.0135 (5) | |
| H8 | 0.1138 | 0.3435 | 0.4324 | 0.016* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.02929 (14) | 0.01733 (14) | 0.01372 (13) | −0.00098 (11) | 0.00552 (10) | −0.00406 (9) |
| O1 | 0.0270 (10) | 0.0133 (8) | 0.0233 (9) | −0.0033 (7) | 0.0058 (8) | 0.0004 (7) |
| O2 | 0.0272 (10) | 0.0228 (9) | 0.0148 (9) | 0.0010 (7) | −0.0020 (7) | 0.0036 (7) |
| N1 | 0.0178 (10) | 0.0113 (10) | 0.0182 (10) | 0.0032 (8) | 0.0079 (8) | 0.0012 (8) |
| C1 | 0.0107 (11) | 0.0190 (12) | 0.0120 (11) | 0.0007 (9) | 0.0032 (9) | −0.0014 (9) |
| C2 | 0.0151 (12) | 0.0119 (12) | 0.0207 (13) | −0.0022 (9) | 0.0081 (10) | −0.0021 (9) |
| C3 | 0.0178 (12) | 0.0158 (12) | 0.0207 (13) | −0.0014 (10) | 0.0074 (10) | 0.0057 (10) |
| C4 | 0.0211 (13) | 0.0227 (14) | 0.0122 (12) | −0.0046 (10) | 0.0042 (10) | −0.0008 (10) |
| C5 | 0.0173 (12) | 0.0146 (12) | 0.0161 (12) | −0.0010 (9) | 0.0056 (10) | −0.0023 (9) |
| C6 | 0.0099 (11) | 0.0113 (11) | 0.0148 (12) | 0.0014 (8) | 0.0046 (9) | 0.0015 (9) |
| C7 | 0.0119 (11) | 0.0150 (12) | 0.0124 (11) | 0.0032 (9) | 0.0037 (9) | 0.0005 (9) |
| C8 | 0.0164 (12) | 0.0132 (12) | 0.0111 (12) | 0.0047 (9) | 0.0050 (9) | 0.0037 (9) |
| Br1—C1 | 1.906 (2) | C3—H3 | 0.9500 |
| O1—N1 | 1.239 (2) | C4—C5 | 1.387 (3) |
| O2—N1 | 1.234 (2) | C4—H4 | 0.9500 |
| N1—C8 | 1.444 (3) | C5—C6 | 1.401 (3) |
| C1—C2 | 1.394 (3) | C5—H5 | 0.9500 |
| C1—C6 | 1.402 (3) | C6—C7 | 1.468 (3) |
| C2—C3 | 1.377 (3) | C7—C8 | 1.328 (3) |
| C2—H2 | 0.9500 | C7—H7 | 0.9500 |
| C3—C4 | 1.395 (3) | C8—H8 | 0.9500 |
| O2—N1—O1 | 123.39 (19) | C3—C4—H4 | 120.1 |
| O2—N1—C8 | 119.86 (18) | C4—C5—C6 | 121.8 (2) |
| O1—N1—C8 | 116.75 (18) | C4—C5—H5 | 119.1 |
| C2—C1—C6 | 121.6 (2) | C6—C5—H5 | 119.1 |
| C2—C1—Br1 | 116.81 (16) | C1—C6—C5 | 116.97 (19) |
| C6—C1—Br1 | 121.57 (16) | C1—C6—C7 | 121.70 (19) |
| C3—C2—C1 | 119.9 (2) | C5—C6—C7 | 121.31 (19) |
| C3—C2—H2 | 120.0 | C8—C7—C6 | 124.4 (2) |
| C1—C2—H2 | 120.0 | C8—C7—H7 | 117.8 |
| C2—C3—C4 | 119.9 (2) | C6—C7—H7 | 117.8 |
| C2—C3—H3 | 120.0 | C7—C8—N1 | 120.14 (19) |
| C4—C3—H3 | 120.0 | C7—C8—H8 | 119.9 |
| C5—C4—C3 | 119.7 (2) | N1—C8—H8 | 119.9 |
| C5—C4—H4 | 120.1 | ||
| C6—C1—C2—C3 | 0.9 (3) | Br1—C1—C6—C7 | −2.4 (3) |
| Br1—C1—C2—C3 | −178.25 (16) | C4—C5—C6—C1 | −1.0 (3) |
| C1—C2—C3—C4 | −1.0 (3) | C4—C5—C6—C7 | −179.4 (2) |
| C2—C3—C4—C5 | 0.2 (3) | C1—C6—C7—C8 | 168.8 (2) |
| C3—C4—C5—C6 | 0.9 (4) | C5—C6—C7—C8 | −13.0 (3) |
| C2—C1—C6—C5 | 0.1 (3) | C6—C7—C8—N1 | 179.9 (2) |
| Br1—C1—C6—C5 | 179.22 (16) | O2—N1—C8—C7 | −10.9 (3) |
| C2—C1—C6—C7 | 178.5 (2) | O1—N1—C8—C7 | 168.8 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C8H6BrNO2 |
| Mr | 228.05 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 113 |
| a, b, c (Å) | 6.9570 (18), 15.646 (2), 7.9470 (13) |
| β (°) | 109.336 (5) |
| V (Å3) | 816.2 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 4.99 |
| Crystal size (mm) | 0.20 × 0.18 × 0.16 |
| Data collection | |
| Diffractometer | Rigaku Saturn724 CCD |
| Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
| Tmin, Tmax | 0.435, 0.502 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 10346, 1945, 1466 |
| Rint | 0.042 |
| (sin θ/λ)max (Å−1) | 0.657 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.056, 1.08 |
| No. of reflections | 1945 |
| No. of parameters | 109 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.78 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2005).
Acknowledgements
This work was supported financially by the Start-up Foundation of North University of China and the Youth Foundation of North University of China.
References
Ballini, R., Castagnani, R. & Petrini, M. (1992). J. Org. Chem. 57, 2160–2162. CrossRef CAS Web of Science Google Scholar
Barret, A. G. M. & Graboski, G. G. (1986). Chem. Rev. 86, 751–762. Google Scholar
Berner, O. M., Tedeschi, L. & Enders, D. (2002). Eur. J. Org. Chem. pp. 1877–1894. CrossRef Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc. The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Nitro-olefins are useful building blocks in organic synthesis (Barret et al., 1986). Furthermore, the charater of these compounds as electron-deficient alkenes allows easy 1,4-addtion reactions and this opens the way to synthetically useful C—C and C—X (X = N, O) bond-forming reactions (Berner et al. (2002), Ballini et al. (1992)). The title compound, (I), belongs to the class of fuctionalized nitroolefins.
As shown in Fig. 1, the dihedral angle between carbon double bond and phenyl groups is 12.2 (2) °. As shown in Fig. 2, the crystal packing shows the weak O···Br intermolecular interactions.