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Acta Cryst. (2007). E63, o3969    [ doi:10.1107/S1600536807042055 ]

2,3-Bis(3-nitrophenyl)quinoxaline

P. Lei, Z.-Z. Hu, C.-P. Wang, X. Chen and Z.-Q. Zhang

Abstract top

The title compound, C20H12N4O4, contains two benzene rings ortho bonded to a quinoxaline nucleus. The dihedral angle between the benzene rings is 59.2 (4)°. The two benzene rings adopt a trans configuration with respect to the quinoxaline plane. The formal C-C [sigma]-bond substituted by nitrophenyl groups is shorter than normal C-C bonds and the C(benzene)-C(quinoxaline) bonds. These features are consistent with electron delocalization over the whole molecule.

Comment top

Functionalized quinoxalines possess a wide range of biological activities, including anticancer (Lindsley et al., 2005), antiviral (Loriga et al., 1997), and antibacterial activity (Seitz et al., 2002), and have also be reported to be kinase inhibitors (He et al., 2003). Herein we report the synthesis and molecular structure of a quinoxaline derivative, (I).

In the molecular structure of (I), the two benzene rings attached to the quinoxaline nucleus make a dihedral angle of 59.2 (4)°. The quinoxaline ring is approximately planar, with a r.m.s. deviation of 0.0341 (5) Å. The two benzene rings make dihedral angles of 26.7 (4) and 58.1 (4)°, respectively, with the planar quinoxaline system. The C6—C7 and C14—C15 bond lengths linking nitrophenyl groups to the quionxaline nucleus (Table 1), are slightly shorter than the normal C—C σ bonds, as a consequence of the delocalization over the aromatic rings. Short bond length is also observed for the C7—C14 bond.

The structure of a related molecule, 2,3-diphenylquinoxaline, has been reported previously (Cantalupo et al., 2006; Rajnikant et al., 2006).

Related literature top

For related literature, see: Cantalupo et al. (2006); He et al. (2003); Lindsley et al. (2005); Loriga et al. (1997); Rajnikant et al. (2006); Seitz et al. (2002).

Experimental top

A suspension of 1,2-bis(3-nitrophenyl)ethane-1,2-dione (0.8 mmol) and benzene-1,2-diamine (1.0 mmol) in acetic acid (AcOH, 3 ml) was refluxed for 0.5 h. The mixture was poured into ice-water and a white precipitate was formed. The mixture was neutralized using saturated NaHCO3 solution. The resulting precipitate was filtered, washed with water, dried and purified by recrystallization using a mixture of ethyl acetate/petroleum ether, giving the target product as light yellow floccules in 35% yield. Colorless crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform/ethanol (1:15 v/v).

Refinement top

All H atoms were positioned geometrically and refined as riding on their carrier atom with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(carrier C atom).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. View of the molecule of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 35% probability level.
2,3-Bis(3-nitrophenyl)quinoxaline top
Crystal data top
C20H12N4O4Dx = 1.473 Mg m−3
Mr = 372.34Melting point: 484 K
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2243 reflections
a = 12.807 (3) Åθ = 2.3–22.5º
b = 7.6160 (15) ŵ = 0.11 mm−1
c = 34.430 (7) ÅT = 294 (2) K
V = 3358.2 (12) Å3Plate, colourless
Z = 80.22 × 0.18 × 0.12 mm
F000 = 1536
Data collection top
Bruker SMART 1000
diffractometer		2948 independent reflections
Radiation source: fine-focus sealed tube1533 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.083
T = 294(2) Kθmax = 25.0º
φ and ω scansθmin = 1.2º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −12→15
Tmin = 0.977, Tmax = 0.983k = −9→6
13448 measured reflectionsl = −33→40
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.190  w = 1/[σ2(Fo2) + (0.0892P)2 + 1.3718P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2948 reflectionsΔρmax = 0.39 e Å−3
253 parametersΔρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C20H12N4O4V = 3358.2 (12) Å3
Mr = 372.34Z = 8
Orthorhombic, PbcaMo Kα
a = 12.807 (3) ŵ = 0.11 mm−1
b = 7.6160 (15) ÅT = 294 (2) K
c = 34.430 (7) Å0.22 × 0.18 × 0.12 mm
Data collection top
Bruker SMART 1000
diffractometer		2948 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1533 reflections with I > 2σ(I)
Tmin = 0.977, Tmax = 0.983Rint = 0.083
13448 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057253 parameters
wR(F2) = 0.190H-atom parameters constrained
S = 1.01Δρmax = 0.39 e Å−3
2948 reflectionsΔρmin = −0.25 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.7566 (4)1.1964 (7)−0.02595 (10)0.1310 (17)
O20.8690 (3)1.0826 (5)0.01110 (10)0.0870 (11)
O30.2285 (3)0.8632 (5)0.18938 (10)0.0883 (11)
O40.1405 (3)0.7078 (6)0.14923 (13)0.1201 (16)
N10.7804 (4)1.1237 (5)0.00377 (10)0.0723 (12)
N20.7785 (2)0.8778 (4)0.13906 (8)0.0410 (8)
N30.6311 (2)0.7105 (4)0.18590 (8)0.0425 (8)
N40.2227 (3)0.7670 (6)0.16106 (13)0.0711 (11)
C10.7236 (3)0.9972 (5)0.06500 (10)0.0427 (9)
H10.79020.95010.06770.051*
C20.6987 (3)1.0903 (5)0.03248 (11)0.0510 (10)
C30.6010 (4)1.1591 (5)0.02666 (13)0.0622 (12)
H3A0.58431.21630.00360.075*
C40.5285 (3)1.1413 (5)0.05580 (13)0.0639 (12)
H4A0.46251.19080.05310.077*
C50.5536 (3)1.0506 (5)0.08894 (12)0.0532 (11)
H50.50401.04130.10860.064*
C60.6500 (3)0.9724 (5)0.09413 (10)0.0414 (9)
C70.6801 (3)0.8727 (4)0.12936 (9)0.0371 (9)
C80.8071 (3)0.7959 (5)0.17225 (10)0.0410 (9)
C90.9120 (3)0.7918 (5)0.18301 (12)0.0526 (10)
H90.96210.84340.16710.063*
C100.9413 (3)0.7126 (6)0.21664 (12)0.0607 (12)
H101.01150.70930.22350.073*
C110.8674 (4)0.6365 (6)0.24082 (12)0.0590 (11)
H110.88840.58250.26370.071*
C120.7646 (3)0.6403 (5)0.23127 (10)0.0526 (11)
H120.71560.58990.24780.063*
C130.7320 (3)0.7196 (5)0.19665 (9)0.0397 (9)
C140.6066 (3)0.7777 (5)0.15223 (10)0.0402 (9)
C150.5015 (3)0.7331 (5)0.13689 (10)0.0449 (9)
C160.4938 (3)0.6437 (5)0.10190 (11)0.0560 (11)
H160.55440.61620.08830.067*
C170.3983 (4)0.5947 (6)0.08668 (12)0.0633 (12)
H170.39460.53420.06330.076*
C180.3105 (4)0.6358 (6)0.10632 (13)0.0610 (12)
H180.24560.60470.09640.073*
C190.3170 (3)0.7230 (5)0.14073 (12)0.0514 (10)
C200.4127 (3)0.7711 (5)0.15701 (11)0.0487 (10)
H200.41580.82740.18090.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.141 (3)0.177 (4)0.075 (2)0.057 (3)0.027 (2)0.065 (3)
O20.077 (2)0.101 (3)0.083 (2)0.012 (2)0.027 (2)0.022 (2)
O30.071 (3)0.119 (3)0.075 (2)0.018 (2)0.0175 (19)0.005 (2)
O40.036 (2)0.145 (4)0.180 (4)−0.012 (2)0.004 (2)−0.018 (3)
N10.093 (3)0.074 (3)0.050 (2)0.020 (2)0.012 (2)0.015 (2)
N20.036 (2)0.0402 (18)0.0466 (18)0.0011 (14)0.0006 (15)−0.0021 (14)
N30.041 (2)0.0475 (18)0.0390 (17)−0.0006 (15)−0.0014 (14)−0.0019 (15)
N40.053 (3)0.077 (3)0.083 (3)0.006 (2)0.003 (2)0.020 (2)
C10.042 (2)0.040 (2)0.046 (2)−0.0001 (17)−0.0010 (19)−0.0046 (17)
C20.065 (3)0.046 (2)0.042 (2)−0.003 (2)0.005 (2)0.0032 (19)
C30.068 (3)0.056 (3)0.063 (3)0.002 (2)−0.014 (3)0.012 (2)
C40.048 (3)0.057 (3)0.086 (3)0.007 (2)−0.004 (3)0.017 (2)
C50.041 (2)0.051 (2)0.068 (3)0.004 (2)0.005 (2)0.012 (2)
C60.040 (2)0.039 (2)0.045 (2)−0.0027 (17)−0.0007 (18)−0.0040 (17)
C70.037 (2)0.035 (2)0.039 (2)0.0015 (16)0.0018 (17)−0.0036 (16)
C80.041 (2)0.040 (2)0.042 (2)0.0037 (17)−0.0023 (18)−0.0055 (17)
C90.037 (3)0.056 (2)0.065 (3)0.0005 (19)0.000 (2)0.000 (2)
C100.047 (3)0.068 (3)0.068 (3)0.006 (2)−0.020 (2)0.003 (2)
C110.067 (3)0.061 (3)0.049 (2)0.003 (2)−0.013 (2)0.000 (2)
C120.062 (3)0.052 (3)0.043 (2)−0.004 (2)−0.001 (2)−0.0020 (18)
C130.042 (2)0.041 (2)0.0358 (19)0.0015 (17)0.0007 (18)−0.0053 (16)
C140.035 (2)0.040 (2)0.046 (2)0.0023 (16)0.0030 (18)−0.0037 (17)
C150.043 (3)0.045 (2)0.047 (2)−0.0008 (18)0.0039 (19)0.0084 (18)
C160.049 (3)0.063 (3)0.056 (3)−0.002 (2)−0.002 (2)−0.004 (2)
C170.068 (3)0.066 (3)0.056 (3)−0.003 (2)−0.008 (3)−0.008 (2)
C180.051 (3)0.066 (3)0.066 (3)−0.006 (2)−0.007 (2)0.013 (2)
C190.040 (3)0.052 (2)0.062 (3)0.000 (2)0.007 (2)0.014 (2)
C200.049 (3)0.047 (2)0.050 (2)0.0025 (19)0.004 (2)0.0062 (18)
Geometric parameters (Å, °) top
O1—N11.202 (4)C8—C91.394 (5)
O2—N11.204 (4)C8—C131.403 (5)
O3—N41.222 (5)C9—C101.358 (5)
O4—N41.215 (5)C9—H90.9300
N1—C21.462 (5)C10—C111.387 (6)
N2—C71.304 (4)C10—H100.9300
N2—C81.353 (4)C11—C121.357 (5)
N3—C141.305 (4)C11—H110.9300
N3—C131.346 (4)C12—C131.401 (5)
N4—C191.435 (5)C12—H120.9300
C1—C21.363 (5)C14—C151.485 (5)
C1—C61.389 (5)C15—C201.363 (5)
C1—H10.9300C15—C161.387 (5)
C2—C31.372 (5)C16—C171.382 (5)
C3—C41.373 (6)C16—H160.9300
C3—H3A0.9300C17—C181.349 (5)
C4—C51.372 (5)C17—H170.9300
C4—H4A0.9300C18—C191.361 (6)
C5—C61.383 (5)C18—H180.9300
C5—H50.9300C19—C201.397 (5)
C6—C71.482 (5)C20—H200.9300
C7—C141.425 (5)
O1—N1—O2122.5 (4)C8—C9—H9119.9
O1—N1—C2118.3 (4)C9—C10—C11120.6 (4)
O2—N1—C2119.2 (4)C9—C10—H10119.7
C7—N2—C8117.7 (3)C11—C10—H10119.7
C14—N3—C13117.0 (3)C12—C11—C10120.5 (4)
O4—N4—O3122.9 (4)C12—C11—H11119.7
O4—N4—C19118.6 (5)C10—C11—H11119.7
O3—N4—C19118.5 (4)C11—C12—C13120.3 (4)
C2—C1—C6120.3 (4)C11—C12—H12119.8
C2—C1—H1119.8C13—C12—H12119.8
C6—C1—H1119.8N3—C13—C12119.9 (3)
C1—C2—C3122.2 (4)N3—C13—C8121.0 (3)
C1—C2—N1118.6 (4)C12—C13—C8118.9 (4)
C3—C2—N1119.2 (4)N3—C14—C7122.1 (3)
C2—C3—C4118.2 (4)N3—C14—C15116.4 (3)
C2—C3—H3A120.9C7—C14—C15121.2 (3)
C4—C3—H3A120.9C20—C15—C16119.1 (4)
C5—C4—C3120.0 (4)C20—C15—C14121.8 (3)
C5—C4—H4A120.0C16—C15—C14119.1 (3)
C3—C4—H4A120.0C17—C16—C15121.7 (4)
C4—C5—C6122.2 (4)C17—C16—H16119.2
C4—C5—H5118.9C15—C16—H16119.2
C6—C5—H5118.9C18—C17—C16119.0 (4)
C5—C6—C1117.0 (3)C18—C17—H17120.5
C5—C6—C7124.0 (3)C16—C17—H17120.5
C1—C6—C7119.0 (3)C17—C18—C19119.9 (4)
N2—C7—C14120.8 (3)C17—C18—H18120.0
N2—C7—C6116.4 (3)C19—C18—H18120.0
C14—C7—C6122.8 (3)C18—C19—C20122.1 (4)
N2—C8—C9119.8 (3)C18—C19—N4119.1 (4)
N2—C8—C13120.7 (3)C20—C19—N4118.8 (4)
C9—C8—C13119.5 (3)C15—C20—C19118.2 (4)
C10—C9—C8120.2 (4)C15—C20—H20120.9
C10—C9—H9119.9C19—C20—H20120.9
C6—C1—C2—C3−1.5 (6)C11—C12—C13—C8−0.4 (5)
C6—C1—C2—N1175.8 (3)N2—C8—C13—N36.7 (5)
O1—N1—C2—C1175.5 (4)C9—C8—C13—N3−175.4 (3)
O2—N1—C2—C1−6.6 (6)N2—C8—C13—C12−178.3 (3)
O1—N1—C2—C3−7.2 (6)C9—C8—C13—C12−0.3 (5)
O2—N1—C2—C3170.7 (4)C13—N3—C14—C7−6.3 (5)
C1—C2—C3—C43.8 (6)C13—N3—C14—C15167.0 (3)
N1—C2—C3—C4−173.5 (4)N2—C7—C14—N38.5 (5)
C2—C3—C4—C5−2.5 (6)C6—C7—C14—N3−170.5 (3)
C3—C4—C5—C6−1.0 (6)N2—C7—C14—C15−164.5 (3)
C4—C5—C6—C13.3 (6)C6—C7—C14—C1516.5 (5)
C4—C5—C6—C7−179.7 (4)N3—C14—C15—C2058.2 (5)
C2—C1—C6—C5−2.0 (5)C7—C14—C15—C20−128.4 (4)
C2—C1—C6—C7−179.2 (3)N3—C14—C15—C16−119.1 (4)
C8—N2—C7—C14−2.6 (5)C7—C14—C15—C1654.4 (5)
C8—N2—C7—C6176.5 (3)C20—C15—C16—C171.0 (6)
C5—C6—C7—N2−148.7 (3)C14—C15—C16—C17178.3 (4)
C1—C6—C7—N228.2 (5)C15—C16—C17—C180.4 (6)
C5—C6—C7—C1430.3 (5)C16—C17—C18—C19−0.6 (6)
C1—C6—C7—C14−152.8 (3)C17—C18—C19—C20−0.6 (6)
C7—N2—C8—C9177.5 (3)C17—C18—C19—N4179.5 (4)
C7—N2—C8—C13−4.6 (5)O4—N4—C19—C188.2 (6)
N2—C8—C9—C10178.8 (3)O3—N4—C19—C18−171.3 (4)
C13—C8—C9—C100.8 (6)O4—N4—C19—C20−171.6 (4)
C8—C9—C10—C11−0.6 (6)O3—N4—C19—C208.8 (6)
C9—C10—C11—C12−0.1 (6)C16—C15—C20—C19−2.1 (5)
C10—C11—C12—C130.6 (6)C14—C15—C20—C19−179.3 (3)
C14—N3—C13—C12−176.0 (3)C18—C19—C20—C152.0 (6)
C14—N3—C13—C8−1.0 (5)N4—C19—C20—C15−178.1 (3)
C11—C12—C13—N3174.7 (3)
Selected geometric parameters (Å, °) top
C6—C71.482 (5)C14—C151.485 (5)
C7—C141.425 (5)
N2—C7—C6116.4 (3)N3—C14—C15116.4 (3)
Acknowledgements top

The authors thank Mr Haijun Chi, Mr Yan Dong and Ms Ping Zhou for their assistance in obtaining NMR and MS data.

references
References top

Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Cantalupo, S. A., Salvati, H., McBurney, B., Raju, R., Glagovich, N. M. & Crundwell, G. (2006). J. Chem. Crystallogr. 36, 17–24.

He, W., Myers, M. R., Hanney, B., Spada, A. P., Bilder, G., Galzcinski, H., Amin, D., Needle, S., Page, K., Jayyosi, Z. & Perrone, M. H. (2003). Bioorg. Med. Chem. Lett. 13, 3097–3100.

Lindsley, C. W., Zhao, Z., Leister, W. H., Robinson, R. G., Barnett, S. F., Defeo-Jones, D., Jones, R. E., Hartman, G. D., Huff, J. R., Huber, H. E. & Duggan, M. E. (2005). Bioorg. Med. Chem. Lett. 15, 761–764.

Loriga, M., Piras, S., Sanna, P. & Paglietti, G. (1997). Il Farm., 52, 157–166.

Rajnikant, initials?, Dinesh, initials?, Deshmukh, M. B., Jadhav, S. & Kanwal, P. (2006). Acta Cryst. E62, o2356–o2357.

Seitz, L. E., Suling, W. J. & Reynolds, R. C. (2002). J. Med. Chem. 45, 5604–5606.

Sheldrick, G. M. (1997). SHELXS97. University of Göttingen, Germany.