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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1380.
Published online 2010 May 19. doi:  10.1107/S160053681001723X
PMCID: PMC2979498

2-(4-Bromo­phen­yl)quinoxaline

Abstract

In the title compound, C14H9BrN2, the benzene and quinoxaline rings are almost coplanar [r.m.s. deviation = 0.0285 (3) Å and dihedral angle = 2.1 (2)°].

Related literature

For the synthesis of quinoxaline derivatives, see: Raw et al. (2003 [triangle]); Bhosale et al. (2005 [triangle]). For their applications, see: Brock et al. (1999 [triangle]); Seitz et al. (2002 [triangle]); He et al. (2003 [triangle]). For typical bond lengths in a related structure, see: Rong et al. (2006 [triangle]).

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Object name is e-66-o1380-scheme1.jpg

Experimental

Crystal data

  • C14H9BrN2
  • M r = 285.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1380-efi1.jpg
  • a = 13.959 (3) Å
  • b = 5.9031 (12) Å
  • c = 14.497 (3) Å
  • β = 109.53 (3)°
  • V = 1125.9 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.63 mm−1
  • T = 153 K
  • 0.20 × 0.18 × 0.10 mm

Data collection

  • Rigaku MM-OO7/Saturn 70 CCD area-detector diffractometer
  • Absorption correction: multi-scan (REQAB; Jacobson, 1998 [triangle]) T min = 0.531, T max = 0.713
  • 8910 measured reflections
  • 2683 independent reflections
  • 1763 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.075
  • S = 0.96
  • 2683 reflections
  • 155 parameters
  • H-atom parameters constrained
  • Δρmax = 0.76 e Å−3
  • Δρmin = −0.69 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001723X/zs2039sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001723X/zs2039Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We gratefully acknowledge support of this work by the Key Laboratory Project of Liaoning Province (No. 2008S127) and the Doctoral Starting Foundation of Liaoning Province (No. 20071103).

supplementary crystallographic information

Comment

Quinoxaline derivatives are an important class of nitrogen containing heterocycles, finding use as intermediates in organic synthesis and in addition have been reported as having applications as anticancer, antiviral, and antibacterial agents (Seitz et al., 2002; He et al., 2003) and dyes (Brock et al., 1999). In recent years, many syntheses of quinoxaline derivatives have been reported (Raw et al., 2003; Bhosale et al., 2005). The title compound C14H9BrN2 (I) is one of such quinoxaline derivates which we have synthesized and now report its crystal structure.

The molecular structure of title compound is as shown in Fig.1. The bond lengths and angles are usual for this type of compound (Rong et al., 2006). The dihedral angle between the benzene ring and quinoxaline ring is 2.1 (2)°, which means that the benzene ring and the quinoxaline ring are approximately coplanar with a r.m.s deviation of 0.0285 (3) Å, the Br atom lying in the plane of the substituent benzene ring [r.m.s deviation, 0.0271 (3) Å]. The crystal packing (Fig. 2) is stabilized by van der Waals forces.

Experimental

A suspension of hydrated 2-(4-bromophenyl)-2-oxoacetaldehyde (2.0 mmol) and benzene-1,2-diamine (3.0 mmol) in ethanol (5 ml) was stirred at room temperature with the reaction progress monitored via TLC. The resulting precipitate was filtered off, washed with cold ethanol, dried and purified to give the title compound as a light yellow solid (92.5% yield: m.p. 418 K). Crystals suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1).

Refinement

All H atoms were positioned geometrically and refined as riding with C—H = 0.95 Å and Uiso(H) set equal to 1.2Ueq(carrier atom).

Figures

Fig. 1.
Molecular configuration of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level.
Fig. 2.
The crystal packing of (I), viewed down the c axis.

Crystal data

C14H9BrN2F(000) = 568
Mr = 285.14Dx = 1.682 Mg m3
Monoclinic, P21/cMelting point: 418 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.959 (3) ÅCell parameters from 3221 reflections
b = 5.9031 (12) Åθ = 2.9–27.9°
c = 14.497 (3) ŵ = 3.63 mm1
β = 109.53 (3)°T = 153 K
V = 1125.9 (4) Å3Prism, colorless
Z = 40.20 × 0.18 × 0.10 mm

Data collection

Rigaku Model name? CCD area-detector diffractometer2683 independent reflections
Radiation source: rotating anode1763 reflections with I > 2σ(I)
multilayerRint = 0.052
Detector resolution: 7.31 pixels mm-1θmax = 27.9°, θmin = 2.9°
[var phi] and ω scansh = −18→11
Absorption correction: multi-scan (REQAB; Jacobson, 1998)k = −7→7
Tmin = 0.531, Tmax = 0.713l = −19→19
8910 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.075w = 1/[σ2(Fo2) + (0.0337P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
2683 reflectionsΔρmax = 0.76 e Å3
155 parametersΔρmin = −0.69 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0540 (17)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.460263 (18)1.10538 (4)0.33474 (2)0.03213 (13)
N1−0.12149 (15)0.6560 (3)0.02060 (15)0.0218 (5)
N2−0.05847 (15)1.0700 (3)0.12055 (14)0.0169 (4)
C10.00712 (17)0.9095 (4)0.11986 (16)0.0150 (5)
C2−0.02653 (17)0.7012 (4)0.07034 (17)0.0210 (6)
H20.02290.58820.07360.025*
C3−0.19054 (16)0.8203 (4)0.02054 (16)0.0160 (5)
C4−0.29514 (17)0.7808 (4)−0.02863 (17)0.0204 (6)
H4−0.31680.6436−0.06360.024*
C5−0.36496 (18)0.9398 (4)−0.02576 (17)0.0213 (6)
H5−0.43520.9126−0.05880.026*
C6−0.33379 (19)1.1438 (4)0.02573 (18)0.0229 (6)
H6−0.38331.25230.02790.028*
C7−0.23291 (17)1.1877 (4)0.07274 (17)0.0176 (5)
H7−0.21261.32750.10600.021*
C8−0.15888 (16)1.0252 (4)0.07190 (15)0.0150 (5)
C90.11683 (17)0.9532 (4)0.17107 (16)0.0157 (5)
C100.19145 (17)0.7987 (4)0.16884 (17)0.0186 (5)
H100.17210.66090.13370.022*
C110.29343 (17)0.8427 (4)0.21702 (18)0.0206 (6)
H110.34370.73600.21520.025*
C120.32117 (17)1.0434 (4)0.26773 (17)0.0186 (5)
C130.24914 (17)1.2017 (4)0.27042 (17)0.0196 (5)
H130.26921.34060.30450.023*
C140.14782 (18)1.1554 (4)0.22297 (16)0.0186 (5)
H140.09801.26270.22550.022*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.01429 (15)0.0399 (2)0.03931 (19)−0.00711 (11)0.00519 (12)−0.00733 (13)
N10.0176 (11)0.0191 (10)0.0248 (11)0.0017 (8)0.0021 (9)−0.0045 (9)
N20.0157 (10)0.0175 (10)0.0176 (9)0.0015 (8)0.0054 (9)−0.0003 (8)
C10.0153 (11)0.0153 (12)0.0148 (11)0.0002 (9)0.0058 (10)0.0002 (9)
C20.0158 (12)0.0198 (12)0.0246 (13)0.0035 (10)0.0029 (11)−0.0052 (11)
C30.0148 (12)0.0172 (11)0.0147 (11)0.0002 (9)0.0031 (10)0.0018 (9)
C40.0188 (13)0.0194 (12)0.0193 (11)−0.0026 (10)0.0015 (11)0.0002 (10)
C50.0115 (12)0.0273 (14)0.0216 (12)0.0004 (9)0.0009 (10)0.0039 (10)
C60.0248 (14)0.0213 (13)0.0234 (13)0.0085 (11)0.0090 (12)0.0048 (10)
C70.0188 (12)0.0135 (11)0.0209 (12)0.0022 (10)0.0070 (11)0.0018 (10)
C80.0149 (12)0.0165 (12)0.0141 (11)−0.0005 (9)0.0053 (10)0.0022 (9)
C90.0149 (12)0.0169 (12)0.0151 (11)−0.0009 (9)0.0048 (10)0.0013 (9)
C100.0173 (12)0.0158 (11)0.0227 (12)−0.0020 (10)0.0068 (10)−0.0043 (10)
C110.0156 (12)0.0210 (13)0.0268 (13)0.0021 (10)0.0090 (11)−0.0011 (10)
C120.0124 (11)0.0229 (13)0.0198 (12)−0.0047 (9)0.0045 (10)0.0007 (10)
C130.0212 (13)0.0171 (11)0.0203 (12)−0.0051 (10)0.0068 (11)−0.0018 (10)
C140.0182 (12)0.0200 (13)0.0172 (11)0.0029 (10)0.0055 (11)−0.0018 (10)

Geometric parameters (Å, °)

Br1—C121.894 (2)C6—C71.369 (3)
N1—C21.307 (3)C6—H60.9500
N1—C31.367 (3)C7—C81.413 (3)
N2—C11.320 (3)C7—H70.9500
N2—C81.368 (3)C9—C101.393 (3)
C1—C21.422 (3)C9—C141.400 (3)
C1—C91.484 (3)C10—C111.385 (3)
C2—H20.9500C10—H100.9500
C3—C81.411 (3)C11—C121.379 (3)
C3—C41.414 (3)C11—H110.9500
C4—C51.364 (3)C12—C131.383 (3)
C4—H40.9500C13—C141.378 (3)
C5—C61.407 (3)C13—H130.9500
C5—H50.9500C14—H140.9500
C2—N1—C3116.11 (19)C8—C7—H7120.0
C1—N2—C8116.82 (18)N2—C8—C3121.6 (2)
N2—C1—C2120.8 (2)N2—C8—C7119.4 (2)
N2—C1—C9118.30 (19)C3—C8—C7119.0 (2)
C2—C1—C9120.9 (2)C10—C9—C14118.1 (2)
N1—C2—C1123.9 (2)C10—C9—C1121.96 (19)
N1—C2—H2118.0C14—C9—C1119.9 (2)
C1—C2—H2118.0C11—C10—C9121.1 (2)
N1—C3—C8120.74 (19)C11—C10—H10119.5
N1—C3—C4119.5 (2)C9—C10—H10119.5
C8—C3—C4119.7 (2)C12—C11—C10119.2 (2)
C5—C4—C3119.9 (2)C12—C11—H11120.4
C5—C4—H4120.0C10—C11—H11120.4
C3—C4—H4120.0C11—C12—C13121.2 (2)
C4—C5—C6120.5 (2)C11—C12—Br1119.76 (18)
C4—C5—H5119.7C13—C12—Br1119.03 (17)
C6—C5—H5119.7C14—C13—C12119.1 (2)
C7—C6—C5120.7 (2)C14—C13—H13120.4
C7—C6—H6119.7C12—C13—H13120.4
C5—C6—H6119.7C13—C14—C9121.3 (2)
C6—C7—C8120.1 (2)C13—C14—H14119.4
C6—C7—H7120.0C9—C14—H14119.4
C8—N2—C1—C20.1 (3)C4—C3—C8—C7−0.2 (3)
C8—N2—C1—C9179.40 (19)C6—C7—C8—N2−179.0 (2)
C3—N1—C2—C1−2.1 (3)C6—C7—C8—C31.2 (3)
N2—C1—C2—N12.2 (4)N2—C1—C9—C10−176.0 (2)
C9—C1—C2—N1−177.1 (2)C2—C1—C9—C103.3 (4)
C2—N1—C3—C80.0 (3)N2—C1—C9—C143.5 (3)
C2—N1—C3—C4−177.7 (2)C2—C1—C9—C14−177.2 (2)
N1—C3—C4—C5177.3 (2)C14—C9—C10—C110.4 (4)
C8—C3—C4—C5−0.4 (3)C1—C9—C10—C11179.9 (2)
C3—C4—C5—C60.1 (4)C9—C10—C11—C12−0.2 (4)
C4—C5—C6—C70.8 (4)C10—C11—C12—C13−0.6 (4)
C5—C6—C7—C8−1.5 (4)C10—C11—C12—Br1179.59 (19)
C1—N2—C8—C3−2.2 (3)C11—C12—C13—C141.2 (4)
C1—N2—C8—C7178.0 (2)Br1—C12—C13—C14−179.02 (17)
N1—C3—C8—N22.2 (3)C12—C13—C14—C9−1.0 (4)
C4—C3—C8—N2179.9 (2)C10—C9—C14—C130.2 (4)
N1—C3—C8—C7−177.9 (2)C1—C9—C14—C13−179.4 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZS2039).

References

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