Acta Cryst. (2007). E63, o4165 [ doi:10.1107/S1600536807046533 ]
In the title compound, C14H12BrN3O3, the two benzene rings are slightly twisted, making a dihedral angle of 9.9 (3)°. The crystal packing is stabilized by weak intermolecular N-H
O and C-HO hydrogen bonds.
4-Nitrophenylhydrazine (1 mmol, 0.153 g) was dissolved in anhydrous methanol, H2SO4 (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, 3-Bromo-4-methoxybenzaldehyde (1 mmol 0.215 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in dichloromethane, brown single crystals of (I) was obtained after 1 d.
All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93Å (aromatic) or 0.96Å (methy) and N—H = 0.86Å with Uiso(H) = 1.2Ueq(Caromatic, N) or Uiso(H) = 1.5Ueq(methyl).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
![[Figure 1]](./dn3064fig1thm.gif)
| Fig. 1. Molecular view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii. |
![[Figure 2]](./dn3064fig2thm.gif)
| Fig. 2. Partial packing view of (I), showing the intermolecular hydrogen bonds as dashed lines. |
| C14H12BrN3O3 | F000 = 1408 |
| Mr = 350.18 | Dx = 1.591 Mg m−3 |
| Orthorhombic, Pccn | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ab 2ac | Cell parameters from 1248 reflections |
| a = 7.2800 (15) Å | θ = 2.5–27.8º |
| b = 14.678 (3) Å | µ = 2.82 mm−1 |
| c = 27.368 (6) Å | T = 298 (2) K |
| V = 2924.4 (10) Å3 | Block, brown |
| Z = 8 | 0.27 × 0.25 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 2980 independent reflections |
| Radiation source: fine-focus sealed tube | 2456 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.060 |
| T = 298(2) K | θmax = 26.5º |
| ω scans | θmin = 2.8º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
| Tmin = 0.486, Tmax = 0.548 | k = −18→18 |
| 30041 measured reflections | l = −34→34 |
| 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)] = 0.091 | H-atom parameters constrained |
| wR(F2) = 0.176 | w = 1/[σ2(Fo2) + (0.045P)2 + 6.3175P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.22 | (Δ/σ)max < 0.001 |
| 2980 reflections | Δρmax = 0.93 e Å−3 |
| 191 parameters | Δρmin = −0.58 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C14H12BrN3O3 | V = 2924.4 (10) Å3 |
| Mr = 350.18 | Z = 8 |
| Orthorhombic, Pccn | Mo Kα |
| a = 7.2800 (15) Å | µ = 2.82 mm−1 |
| b = 14.678 (3) Å | T = 298 (2) K |
| c = 27.368 (6) Å | 0.27 × 0.25 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 2980 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2456 reflections with I > 2σ(I) |
| Tmin = 0.486, Tmax = 0.548 | Rint = 0.060 |
| 30041 measured reflections |
| R[F2 > 2σ(F2)] = 0.091 | 191 parameters |
| wR(F2) = 0.176 | H-atom parameters constrained |
| S = 1.22 | Δρmax = 0.93 e Å−3 |
| 2980 reflections | Δρmin = −0.58 e Å−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 | ||
| Br1 | 0.11817 (15) | 0.97770 (5) | 0.17684 (2) | 0.1058 (4) | |
| O1 | 0.3606 (7) | 1.1359 (3) | 0.58357 (17) | 0.0930 (14) | |
| O2 | 0.4495 (6) | 1.2106 (3) | 0.51958 (19) | 0.0857 (13) | |
| O3 | 0.0204 (7) | 0.7930 (3) | 0.14235 (15) | 0.0887 (14) | |
| N1 | 0.3772 (7) | 1.1431 (3) | 0.5392 (2) | 0.0687 (13) | |
| N2 | 0.1160 (7) | 0.8638 (3) | 0.42050 (15) | 0.0642 (12) | |
| H2 | 0.0786 | 0.8142 | 0.4340 | 0.077* | |
| N3 | 0.1076 (6) | 0.8735 (3) | 0.37049 (16) | 0.0630 (12) | |
| C1 | 0.3092 (7) | 1.0709 (4) | 0.50809 (19) | 0.0556 (13) | |
| C2 | 0.2439 (8) | 0.9916 (4) | 0.5293 (2) | 0.0602 (13) | |
| H2A | 0.2421 | 0.9849 | 0.5630 | 0.072* | |
| C3 | 0.1816 (7) | 0.9227 (4) | 0.49932 (18) | 0.0573 (13) | |
| H3 | 0.1378 | 0.8690 | 0.5131 | 0.069* | |
| C4 | 0.1836 (7) | 0.9327 (3) | 0.44878 (18) | 0.0509 (12) | |
| C5 | 0.2542 (8) | 1.0125 (4) | 0.42843 (19) | 0.0591 (13) | |
| H5 | 0.2577 | 1.0196 | 0.3947 | 0.071* | |
| C6 | 0.3184 (8) | 1.0802 (4) | 0.4581 (2) | 0.0615 (14) | |
| H6 | 0.3683 | 1.1328 | 0.4445 | 0.074* | |
| C7 | 0.0422 (8) | 0.8060 (4) | 0.3473 (2) | 0.0666 (15) | |
| H7 | 0.0015 | 0.7557 | 0.3648 | 0.080* | |
| C8 | 0.0284 (8) | 0.8046 (4) | 0.2942 (2) | 0.0622 (14) | |
| C9 | 0.0654 (8) | 0.8806 (4) | 0.2657 (2) | 0.0621 (14) | |
| H9 | 0.0943 | 0.9358 | 0.2805 | 0.075* | |
| C10 | 0.0594 (8) | 0.8745 (4) | 0.2153 (2) | 0.0648 (15) | |
| C11 | 0.0189 (8) | 0.7920 (4) | 0.1923 (2) | 0.0656 (15) | |
| C12 | −0.0173 (9) | 0.7173 (4) | 0.2203 (3) | 0.0802 (19) | |
| H12 | −0.0449 | 0.6620 | 0.2055 | 0.096* | |
| C13 | −0.0130 (9) | 0.7237 (4) | 0.2705 (2) | 0.0745 (17) | |
| H13 | −0.0388 | 0.6722 | 0.2891 | 0.089* | |
| C14 | −0.0039 (13) | 0.7075 (5) | 0.1180 (3) | 0.112 (3) | |
| H14A | 0.0900 | 0.6658 | 0.1284 | 0.167* | |
| H14B | 0.0044 | 0.7163 | 0.0833 | 0.167* | |
| H14C | −0.1224 | 0.6830 | 0.1260 | 0.167* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.1924 (10) | 0.0635 (4) | 0.0616 (4) | 0.0057 (5) | −0.0070 (5) | −0.0025 (3) |
| O1 | 0.119 (4) | 0.090 (3) | 0.069 (3) | −0.005 (3) | −0.008 (3) | −0.017 (2) |
| O2 | 0.091 (3) | 0.057 (2) | 0.108 (3) | −0.012 (2) | −0.009 (3) | −0.005 (2) |
| O3 | 0.126 (4) | 0.075 (3) | 0.064 (2) | 0.023 (3) | −0.029 (3) | −0.030 (2) |
| N1 | 0.063 (3) | 0.061 (3) | 0.082 (4) | 0.008 (3) | −0.007 (3) | −0.009 (3) |
| N2 | 0.082 (3) | 0.059 (3) | 0.052 (2) | −0.010 (3) | −0.002 (2) | 0.008 (2) |
| N3 | 0.071 (3) | 0.067 (3) | 0.051 (2) | −0.003 (2) | −0.003 (2) | 0.002 (2) |
| C1 | 0.053 (3) | 0.052 (3) | 0.062 (3) | 0.006 (2) | −0.011 (3) | −0.002 (2) |
| C2 | 0.063 (3) | 0.066 (3) | 0.052 (3) | 0.009 (3) | −0.001 (3) | 0.006 (3) |
| C3 | 0.062 (3) | 0.054 (3) | 0.055 (3) | 0.000 (3) | −0.003 (3) | 0.009 (2) |
| C4 | 0.045 (3) | 0.053 (3) | 0.055 (3) | 0.002 (2) | −0.003 (2) | 0.002 (2) |
| C5 | 0.066 (3) | 0.060 (3) | 0.050 (3) | −0.009 (3) | −0.003 (3) | 0.009 (2) |
| C6 | 0.062 (3) | 0.050 (3) | 0.072 (4) | −0.003 (3) | −0.004 (3) | 0.014 (3) |
| C7 | 0.071 (4) | 0.057 (3) | 0.071 (4) | −0.006 (3) | −0.010 (3) | −0.002 (3) |
| C8 | 0.056 (3) | 0.065 (4) | 0.065 (3) | −0.004 (3) | −0.007 (3) | −0.010 (3) |
| C9 | 0.075 (4) | 0.053 (3) | 0.059 (3) | 0.006 (3) | −0.015 (3) | −0.012 (3) |
| C10 | 0.083 (4) | 0.052 (3) | 0.060 (3) | 0.016 (3) | −0.013 (3) | −0.012 (3) |
| C11 | 0.065 (4) | 0.066 (4) | 0.066 (3) | 0.014 (3) | −0.019 (3) | −0.019 (3) |
| C12 | 0.088 (5) | 0.055 (3) | 0.098 (5) | −0.005 (3) | −0.023 (4) | −0.028 (3) |
| C13 | 0.083 (4) | 0.062 (4) | 0.078 (4) | −0.010 (3) | −0.012 (3) | −0.004 (3) |
| C14 | 0.161 (8) | 0.086 (5) | 0.088 (5) | 0.034 (5) | −0.040 (5) | −0.044 (4) |
| Br1—C10 | 1.893 (6) | C5—C6 | 1.366 (7) |
| O1—N1 | 1.226 (6) | C5—H5 | 0.9300 |
| O2—N1 | 1.244 (6) | C6—H6 | 0.9300 |
| O3—C11 | 1.367 (7) | C7—C8 | 1.456 (8) |
| O3—C14 | 1.432 (7) | C7—H7 | 0.9300 |
| N1—C1 | 1.447 (7) | C8—C13 | 1.385 (8) |
| N2—C4 | 1.364 (6) | C8—C9 | 1.389 (8) |
| N2—N3 | 1.377 (6) | C9—C10 | 1.382 (7) |
| N2—H2 | 0.8600 | C9—H9 | 0.9300 |
| N3—C7 | 1.269 (7) | C10—C11 | 1.398 (7) |
| C1—C6 | 1.376 (7) | C11—C12 | 1.363 (9) |
| C1—C2 | 1.384 (7) | C12—C13 | 1.379 (9) |
| C2—C3 | 1.379 (7) | C12—H12 | 0.9300 |
| C2—H2A | 0.9300 | C13—H13 | 0.9300 |
| C3—C4 | 1.391 (7) | C14—H14A | 0.9600 |
| C3—H3 | 0.9300 | C14—H14B | 0.9600 |
| C4—C5 | 1.396 (7) | C14—H14C | 0.9600 |
| C11—O3—C14 | 117.0 (5) | N3—C7—H7 | 118.8 |
| O1—N1—O2 | 122.5 (5) | C8—C7—H7 | 118.8 |
| O1—N1—C1 | 119.1 (5) | C13—C8—C9 | 117.8 (5) |
| O2—N1—C1 | 118.4 (5) | C13—C8—C7 | 119.6 (6) |
| C4—N2—N3 | 120.3 (4) | C9—C8—C7 | 122.4 (5) |
| C4—N2—H2 | 119.9 | C10—C9—C8 | 120.2 (5) |
| N3—N2—H2 | 119.9 | C10—C9—H9 | 119.9 |
| C7—N3—N2 | 115.7 (5) | C8—C9—H9 | 119.9 |
| C6—C1—C2 | 121.1 (5) | C9—C10—C11 | 120.8 (6) |
| C6—C1—N1 | 119.7 (5) | C9—C10—Br1 | 119.7 (4) |
| C2—C1—N1 | 119.2 (5) | C11—C10—Br1 | 119.4 (4) |
| C3—C2—C1 | 118.8 (5) | C12—C11—O3 | 125.0 (5) |
| C3—C2—H2A | 120.6 | C12—C11—C10 | 118.9 (5) |
| C1—C2—H2A | 120.6 | O3—C11—C10 | 116.1 (6) |
| C2—C3—C4 | 120.7 (5) | C11—C12—C13 | 120.1 (5) |
| C2—C3—H3 | 119.7 | C11—C12—H12 | 119.9 |
| C4—C3—H3 | 119.7 | C13—C12—H12 | 119.9 |
| N2—C4—C3 | 118.8 (5) | C12—C13—C8 | 122.0 (6) |
| N2—C4—C5 | 121.9 (5) | C12—C13—H13 | 119.0 |
| C3—C4—C5 | 119.3 (5) | C8—C13—H13 | 119.0 |
| C6—C5—C4 | 120.0 (5) | O3—C14—H14A | 109.5 |
| C6—C5—H5 | 120.0 | O3—C14—H14B | 109.5 |
| C4—C5—H5 | 120.0 | H14A—C14—H14B | 109.5 |
| C5—C6—C1 | 120.2 (5) | O3—C14—H14C | 109.5 |
| C5—C6—H6 | 119.9 | H14A—C14—H14C | 109.5 |
| C1—C6—H6 | 119.9 | H14B—C14—H14C | 109.5 |
| N3—C7—C8 | 122.5 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O2i | 0.86 | 2.19 | 3.035 (6) | 166 |
| C7—H7···O1i | 0.93 | 2.48 | 3.400 (8) | 172 |
| Symmetry codes: (i) x−1/2, y−1/2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O2i | 0.86 | 2.19 | 3.035 (6) | 166 |
| C7—H7···O1i | 0.93 | 2.48 | 3.400 (8) | 172 |
| Symmetry codes: (i) x−1/2, y−1/2, −z+1. |
The authors are grateful to the Startup Fund for PhD Students of the Natural Scientific Research Council? of Zhengzhou University of Light Industry (grant No. 2005001) and the Startup Fund for Masters Students of the Natural Scientific Research Council? of Zhengzhou University of Light Industry (grant No. 000455).
Bruker (1997). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1998). SMART (Version 5.628) and SAINT (Version 6.02). Bruker AXS Inc., Madison, Wisconsin, USA.
Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678–1680.
Sheldrick, G. M. (1996). SADABS. Version 6.10. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
4-Nitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al.,1993). As a continuation of this work, we report the synthesis and crystal structure of the title compound(I).
The 4-nitrophenyl group and the methyl benzene rings areslightly twisted making a dihedral angle of 9.9 (3)° (Fig. 1). The N1/O1/O2 nitro group is co-planar with its attached benzene ring [dihedral angle =1.4 (2)°].
The intermolecular N—H···O and C—H···O hydrogen bonds can help stabilizing the molecular structure·(Table 1, Fig.2)