Acta Cryst. (2009). E65, o1553 [ doi:10.1107/S1600536809021564 ]
The title molecule, C9H8BrNO, approximates a full planar conformation. The interplanar angle between the benzene and five-membered rings of the indoline system is 1.38 (1)°. There is an obvious ![[pi]](/logos/entities/pi_rmgif.gif)
-delocalization involving the N-C=O group in the five-membered ring, which is greater than that involving the N-C![[pdbond]](/logos/entities/z-pdbond_rmgif.gif)
C(benzene) group.
1-Methylindolin-2-one (0.50 g) was dissolved in acetonitrile (10 ml). After cooling the mixture to 263 K, an acetonitrile solution of NBS (0.60 g) was slowly added. After stirring for 24 h., the mixture was poured into ice water and further stirred for 1 h. The solution was extracted with chloroform and dried over Na2SO4. After removing the solvent, the crude product was purified by recrystallization from ethanol, affording the title compound, (I) (0.58 g, 76%). Then the compound (I) was dissolved in a mixture of solvents, dichloromethane and isopropyl ether, and pink block crystals were formed on slow evaporation at room temperature over one week.
All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.93 (aromatic CH), 0.97 (CH2 groups) or 0.96 Å (CH3 group). Their isotropic displacement parameters were set to 1.2 times (1.5 times for the methyl group) the equivalent displacement parameter of their parent atoms.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./bh2231fig1thm.gif)
| Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./bh2231fig2thm.gif)
| Fig. 2. A a axis view of the molecular packing of (I). |
| C9H8BrNO | F(000) = 448 |
| Mr = 226.07 | Dx = 1.714 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2899 reflections |
| a = 10.5134 (4) Å | θ = 2.7–27.5° |
| b = 11.0926 (4) Å | µ = 4.64 mm−1 |
| c = 7.7168 (3) Å | T = 293 K |
| β = 103.229 (2)° | Block, pink |
| V = 876.06 (6) Å3 | 0.47 × 0.45 × 0.44 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 2012 independent reflections |
| Radiation source: fine-focus sealed tube | 1655 reflections with I > 2σ(I) |
| graphite | Rint = 0.022 |
| φ and ω scans | θmax = 27.5°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −13→10 |
| Tmin = 0.122, Tmax = 0.130 | k = −11→14 |
| 6684 measured reflections | l = −10→10 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.03P)2 + 0.5204P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 2012 reflections | Δρmax = 0.37 e Å−3 |
| 111 parameters | Δρmin = −0.49 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 constraints | Extinction coefficient: 0.0099 (11) |
| Primary atom site location: structure-invariant direct methods |
| C9H8BrNO | V = 876.06 (6) Å3 |
| Mr = 226.07 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.5134 (4) Å | µ = 4.64 mm−1 |
| b = 11.0926 (4) Å | T = 293 K |
| c = 7.7168 (3) Å | 0.47 × 0.45 × 0.44 mm |
| β = 103.229 (2)° |
| Bruker APEXII CCD area-detector diffractometer | 2012 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1655 reflections with I > 2σ(I) |
| Tmin = 0.122, Tmax = 0.130 | Rint = 0.022 |
| 6684 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
| wR(F2) = 0.071 | Δρmax = 0.37 e Å−3 |
| S = 1.06 | Δρmin = −0.49 e Å−3 |
| 2012 reflections | Absolute structure: ? |
| 111 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.28547 (2) | 0.07936 (3) | 0.20946 (4) | 0.04945 (13) | |
| C1 | 0.4602 (2) | 0.0991 (2) | 0.1860 (3) | 0.0355 (5) | |
| C2 | 0.5537 (2) | 0.0170 (2) | 0.2694 (3) | 0.0374 (5) | |
| H2 | 0.5316 | −0.0460 | 0.3366 | 0.045* | |
| C3 | 0.6793 (2) | 0.0308 (2) | 0.2506 (3) | 0.0329 (5) | |
| C4 | 0.7111 (2) | 0.1265 (2) | 0.1505 (3) | 0.0316 (5) | |
| C5 | 0.6183 (2) | 0.2080 (2) | 0.0666 (3) | 0.0400 (6) | |
| H5 | 0.6401 | 0.2710 | −0.0006 | 0.048* | |
| C6 | 0.4907 (2) | 0.1926 (2) | 0.0858 (3) | 0.0399 (6) | |
| H6 | 0.4258 | 0.2460 | 0.0306 | 0.048* | |
| C7 | 0.8012 (3) | −0.0418 (2) | 0.3173 (4) | 0.0435 (6) | |
| H7A | 0.7903 | −0.1238 | 0.2725 | 0.052* | |
| H7B | 0.8244 | −0.0438 | 0.4464 | 0.052* | |
| C8 | 0.9037 (2) | 0.0246 (2) | 0.2444 (3) | 0.0404 (6) | |
| C9 | 0.9086 (3) | 0.2039 (3) | 0.0514 (4) | 0.0537 (7) | |
| H9A | 0.9993 | 0.1827 | 0.0715 | 0.081* | |
| H9B | 0.9006 | 0.2850 | 0.0908 | 0.081* | |
| H9C | 0.8688 | 0.1978 | −0.0733 | 0.081* | |
| N1 | 0.84354 (19) | 0.12225 (19) | 0.1502 (3) | 0.0360 (4) | |
| O1 | 1.01834 (18) | −0.0009 (2) | 0.2635 (3) | 0.0580 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.03020 (16) | 0.0645 (2) | 0.05570 (18) | −0.00283 (13) | 0.01405 (11) | −0.01295 (13) |
| C1 | 0.0260 (11) | 0.0432 (15) | 0.0375 (11) | −0.0013 (10) | 0.0077 (9) | −0.0084 (10) |
| C2 | 0.0390 (13) | 0.0348 (13) | 0.0409 (12) | −0.0030 (11) | 0.0142 (10) | 0.0002 (10) |
| C3 | 0.0326 (12) | 0.0315 (12) | 0.0343 (11) | −0.0007 (10) | 0.0068 (9) | −0.0015 (9) |
| C4 | 0.0315 (12) | 0.0321 (12) | 0.0313 (11) | −0.0028 (10) | 0.0076 (9) | −0.0044 (9) |
| C5 | 0.0439 (14) | 0.0339 (14) | 0.0441 (13) | −0.0008 (11) | 0.0136 (11) | 0.0049 (10) |
| C6 | 0.0354 (13) | 0.0387 (14) | 0.0425 (13) | 0.0073 (11) | 0.0027 (10) | −0.0004 (11) |
| C7 | 0.0353 (14) | 0.0452 (15) | 0.0499 (14) | 0.0056 (11) | 0.0098 (11) | 0.0097 (12) |
| C8 | 0.0338 (14) | 0.0463 (15) | 0.0415 (13) | 0.0003 (11) | 0.0093 (10) | −0.0034 (11) |
| C9 | 0.0457 (16) | 0.0552 (18) | 0.0667 (18) | −0.0071 (13) | 0.0263 (14) | 0.0092 (14) |
| N1 | 0.0329 (11) | 0.0388 (11) | 0.0382 (10) | −0.0035 (9) | 0.0121 (8) | 0.0001 (9) |
| O1 | 0.0322 (11) | 0.0747 (15) | 0.0686 (12) | 0.0084 (10) | 0.0147 (9) | 0.0060 (11) |
| Br1—C1 | 1.900 (2) | C6—H6 | 0.9300 |
| C1—C6 | 1.375 (4) | C7—C8 | 1.515 (4) |
| C1—C2 | 1.386 (3) | C7—H7A | 0.9700 |
| C2—C3 | 1.370 (3) | C7—H7B | 0.9700 |
| C2—H2 | 0.9300 | C8—O1 | 1.214 (3) |
| C3—C4 | 1.398 (3) | C8—N1 | 1.376 (3) |
| C3—C7 | 1.502 (3) | C9—N1 | 1.451 (3) |
| C4—C5 | 1.377 (3) | C9—H9A | 0.9600 |
| C4—N1 | 1.394 (3) | C9—H9B | 0.9600 |
| C5—C6 | 1.393 (3) | C9—H9C | 0.9600 |
| C5—H5 | 0.9300 | ||
| C6—C1—C2 | 121.7 (2) | C3—C7—C8 | 103.6 (2) |
| C6—C1—Br1 | 119.70 (18) | C3—C7—H7A | 111.0 |
| C2—C1—Br1 | 118.56 (18) | C8—C7—H7A | 111.0 |
| C3—C2—C1 | 118.4 (2) | C3—C7—H7B | 111.0 |
| C3—C2—H2 | 120.8 | C8—C7—H7B | 111.0 |
| C1—C2—H2 | 120.8 | H7A—C7—H7B | 109.0 |
| C2—C3—C4 | 120.1 (2) | O1—C8—N1 | 124.9 (2) |
| C2—C3—C7 | 132.2 (2) | O1—C8—C7 | 127.8 (3) |
| C4—C3—C7 | 107.7 (2) | N1—C8—C7 | 107.4 (2) |
| C5—C4—N1 | 128.4 (2) | N1—C9—H9A | 109.5 |
| C5—C4—C3 | 121.7 (2) | N1—C9—H9B | 109.5 |
| N1—C4—C3 | 109.9 (2) | H9A—C9—H9B | 109.5 |
| C4—C5—C6 | 117.7 (2) | N1—C9—H9C | 109.5 |
| C4—C5—H5 | 121.1 | H9A—C9—H9C | 109.5 |
| C6—C5—H5 | 121.1 | H9B—C9—H9C | 109.5 |
| C1—C6—C5 | 120.4 (2) | C8—N1—C4 | 111.38 (19) |
| C1—C6—H6 | 119.8 | C8—N1—C9 | 123.7 (2) |
| C5—C6—H6 | 119.8 | C4—N1—C9 | 124.8 (2) |
| C6—C1—C2—C3 | 0.1 (4) | C2—C3—C7—C8 | 179.2 (3) |
| Br1—C1—C2—C3 | 179.31 (18) | C4—C3—C7—C8 | 0.4 (3) |
| C1—C2—C3—C4 | 0.6 (3) | C3—C7—C8—O1 | −179.9 (3) |
| C1—C2—C3—C7 | −178.2 (2) | C3—C7—C8—N1 | 0.4 (3) |
| C2—C3—C4—C5 | −0.9 (4) | O1—C8—N1—C4 | 179.3 (2) |
| C7—C3—C4—C5 | 178.1 (2) | C7—C8—N1—C4 | −1.0 (3) |
| C2—C3—C4—N1 | 180.0 (2) | O1—C8—N1—C9 | 4.0 (4) |
| C7—C3—C4—N1 | −1.0 (3) | C7—C8—N1—C9 | −176.2 (2) |
| N1—C4—C5—C6 | 179.5 (2) | C5—C4—N1—C8 | −177.7 (2) |
| C3—C4—C5—C6 | 0.5 (3) | C3—C4—N1—C8 | 1.3 (3) |
| C2—C1—C6—C5 | −0.5 (4) | C5—C4—N1—C9 | −2.6 (4) |
| Br1—C1—C6—C5 | −179.67 (18) | C3—C4—N1—C9 | 176.5 (2) |
| C4—C5—C6—C1 | 0.2 (4) |
| C3—C4 | 1.398 (3) | C8—O1 | 1.214 (3) |
| C4—N1 | 1.394 (3) | C8—N1 | 1.376 (3) |
This work was supported by the Scientific Research Foundation of Northwest A&F University (grant No. 2111020828).
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.
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Frohner, W., Monse, B., Braxmeier, T. M., Casiraghi, L., Sahagun, H. & Seneci, P. (2005). Org. Lett. 7, 4573–4576.
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Xie, J., Sun, J., Zhang, G., Houghten, R. A. & Yu, Y. (2007). J. Comb. Chem. 9, 566–568.
Indole-2-one derivatives have been widely explored due to their wide range of biological activities (Frohner et al., 2005; Xie et al., 2007). Indole-2-one may also be used as a precuesor for synthesizing organic lighting compounds because of its perfect planar conformation. In the course of exploring new luminescent compounds, we obtained an intermediate compound 5-bromo-1-methylindolin-2-one (I). Here we report the structure and synthesis of (I).
The molecule lies approximately in a plane (Fig. 1). The interplanar angle between the benzene group and the five-membered ring is 1.38 (1)° and the maximum displacement from the least-squares plane defined by all the 9 atoms of the indoline framework is 0.057 (3) Å for atom C9. The alternating long and short bond lengths are observed in the benzene ring: C1—C2 = 1.386 (3), C2—C3 = 1.370 (3), C3—C4 = 1.398 (3), C4—C5 = 1.377 (3), C5—C6 = 1.393 (3), C1—C6 = 1.375 (4) Å. The difference among the three C—N bond lengths is obvious, C4—N1 = 1.394 (3), C8—N1 = 1.376 (3), C9—N1 = 1.451 (3) Å, and indicates the presence of an appropriate π delocalization involving the C8—N1 and C8—O1 bonds. The structural conformation of the title molecule (I) is similar to that of 1-methylindolin-2-one (Lipkowski et al., 1995).
The molecules are packed in P21/c space group which is different from that of 1-methylindolin-2-one (Pbca). There are no classic hydrogen bonds in this structure. However, the weak intermolecular interaction C7—H7B···O1 (2 - x, -y, 1 - z), is helpful to the stabilization of the packing (Fig. 2). This intermolecular hydrogen bond is characterized by the bond lengths of 0.97 (C7—H7B) and 2.51 Å (H7B···O1).