Acta Cryst. (2009). E65, o2189 [ doi:10.1107/S160053680903181X ]
The title molecule, C14H10N4O6, crystallizes with one half-molecule in the asymmetric unit; the mid-point of the N-N bond lies on an inversion centre. The nitro and amide groups are twisted with respect to the benzene ring, making dihedral angles of 14.6 (5) and 31.1 (5)°, respectively. In the crystal structure, molecules are linked through N-H
O hydrogen bonding between the imino and carbonyl groups.
4-Nitrobenzohydrazide (0.371 g, 2.0 mmol) and 20 ml chloroform were introduced into a round-bottomed flask at 281 K and stirred. 4-Nitrobenzoyl chloride (0.362 g, 2.0 mmol) was added to the mixture, which was stirred for 2 h at room temperature. A colourless solid product was filtered, and washed three times with ethyl ether. Crystals of the title compound suitable for X-ray structural determination was obtained by slow evaporation a methanol solution in air.
H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 and N—H = 0.86 Å and with Uiso(H) = 1.2 Ueq(C,N).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./xu2587fig1thm.gif)
| Fig. 1. The molecular structure of the title copound, showing 30% probability displacement ellipsoids [symmetry code: (i) 2-x, -y, 1-z]. |
| C14H10N4O6 | F(000) = 340 |
| Mr = 330.26 | Dx = 1.573 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 25 reflections |
| a = 4.7947 (6) Å | θ = 8–12° |
| b = 9.8750 (11) Å | µ = 0.13 mm−1 |
| c = 14.9094 (17) Å | T = 293 K |
| β = 99.05 (3)° | Block, colorless |
| V = 697.13 (14) Å3 | 0.20 × 0.10 × 0.10 mm |
| Z = 2 |
| Enraf–Nonius CAD-4 diffractometer | 673 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.0000 |
| graphite | θmax = 26.0°, θmin = 2.5° |
| ω/2θ scans | h = −5→5 |
| Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
| Tmin = 0.975, Tmax = 0.988 | l = 0→18 |
| 1364 measured reflections | 3 standard reflections every 200 reflections |
| 1364 independent reflections | intensity decay: none |
| 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)] = 0.070 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.220 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.1296P] where P = (Fo2 + 2Fc2)/3 |
| 1364 reflections | (Δ/σ)max < 0.001 |
| 109 parameters | Δρmax = 0.13 e Å−3 |
| 0 restraints | Δρmin = −0.15 e Å−3 |
| C14H10N4O6 | V = 697.13 (14) Å3 |
| Mr = 330.26 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 4.7947 (6) Å | µ = 0.13 mm−1 |
| b = 9.8750 (11) Å | T = 293 K |
| c = 14.9094 (17) Å | 0.20 × 0.10 × 0.10 mm |
| β = 99.05 (3)° |
| Enraf–Nonius CAD-4 diffractometer | 673 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.0000 |
| Tmin = 0.975, Tmax = 0.988 | θmax = 26.0° |
| 1364 measured reflections | 3 standard reflections every 200 reflections |
| 1364 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.070 | H-atom parameters constrained |
| wR(F2) = 0.220 | Δρmax = 0.13 e Å−3 |
| S = 1.10 | Δρmin = −0.15 e Å−3 |
| 1364 reflections | Absolute structure: ? |
| 109 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| O1 | 0.5717 (7) | −0.0146 (4) | 0.4016 (2) | 0.0940 (11) | |
| O2 | 0.8216 (9) | 0.1386 (5) | −0.0278 (3) | 0.1227 (16) | |
| O3 | 1.2216 (11) | 0.2315 (5) | 0.0270 (3) | 0.1219 (15) | |
| N1 | 1.0280 (8) | 0.0187 (4) | 0.4580 (2) | 0.0842 (12) | |
| H1A | 1.1951 | 0.0419 | 0.4498 | 0.101* | |
| N2 | 1.0017 (12) | 0.1715 (5) | 0.0358 (3) | 0.0949 (13) | |
| C1 | 0.8102 (10) | 0.0176 (5) | 0.3890 (3) | 0.0794 (12) | |
| C2 | 0.8783 (10) | 0.0610 (5) | 0.2994 (3) | 0.0775 (12) | |
| C3 | 0.7163 (12) | 0.0022 (6) | 0.2224 (4) | 0.1007 (16) | |
| H3A | 0.5823 | −0.0633 | 0.2297 | 0.121* | |
| C4 | 0.7531 (11) | 0.0399 (6) | 0.1371 (3) | 0.0920 (15) | |
| H4A | 0.6379 | 0.0047 | 0.0865 | 0.110* | |
| C5 | 0.9622 (12) | 0.1304 (6) | 0.1272 (3) | 0.0897 (14) | |
| C6 | 1.1218 (12) | 0.1918 (5) | 0.2030 (4) | 0.0926 (15) | |
| H6A | 1.2522 | 0.2587 | 0.1952 | 0.111* | |
| C7 | 1.0864 (12) | 0.1540 (5) | 0.2868 (3) | 0.0939 (15) | |
| H7A | 1.2021 | 0.1903 | 0.3370 | 0.113* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.087 (2) | 0.124 (3) | 0.0660 (19) | −0.004 (2) | −0.0060 (16) | 0.0027 (19) |
| O2 | 0.140 (3) | 0.145 (4) | 0.070 (2) | 0.015 (3) | −0.024 (2) | 0.009 (3) |
| O3 | 0.156 (4) | 0.117 (3) | 0.090 (3) | −0.013 (3) | 0.010 (3) | 0.015 (2) |
| N1 | 0.077 (2) | 0.102 (3) | 0.065 (2) | −0.004 (2) | −0.0141 (18) | 0.012 (2) |
| N2 | 0.117 (3) | 0.085 (3) | 0.082 (3) | 0.014 (3) | 0.009 (3) | 0.014 (2) |
| C1 | 0.086 (3) | 0.076 (3) | 0.070 (3) | 0.000 (2) | −0.007 (2) | 0.003 (2) |
| C2 | 0.081 (3) | 0.079 (3) | 0.064 (2) | 0.006 (2) | −0.017 (2) | 0.005 (2) |
| C3 | 0.109 (4) | 0.098 (4) | 0.080 (3) | −0.017 (3) | −0.029 (3) | 0.002 (3) |
| C4 | 0.099 (3) | 0.102 (4) | 0.066 (3) | −0.008 (3) | −0.012 (3) | 0.001 (3) |
| C5 | 0.113 (4) | 0.079 (3) | 0.070 (3) | 0.017 (3) | −0.009 (3) | 0.011 (3) |
| C6 | 0.114 (4) | 0.075 (3) | 0.079 (3) | −0.008 (3) | −0.017 (3) | 0.005 (3) |
| C7 | 0.112 (4) | 0.079 (3) | 0.075 (3) | −0.005 (3) | −0.035 (3) | 0.003 (3) |
| O1—C1 | 1.229 (5) | C2—C3 | 1.407 (7) |
| O2—N2 | 1.221 (6) | C3—C4 | 1.362 (7) |
| O3—N2 | 1.234 (5) | C3—H3A | 0.9300 |
| N1—C1 | 1.346 (6) | C4—C5 | 1.368 (7) |
| N1—N1i | 1.372 (7) | C4—H4A | 0.9300 |
| N1—H1A | 0.8600 | C5—C6 | 1.400 (7) |
| N2—C5 | 1.462 (6) | C6—C7 | 1.340 (7) |
| C1—C2 | 1.488 (6) | C6—H6A | 0.9300 |
| C2—C7 | 1.390 (7) | C7—H7A | 0.9300 |
| C1—N1—N1i | 117.1 (5) | C2—C3—H3A | 119.6 |
| C1—N1—H1A | 121.5 | C3—C4—C5 | 119.0 (5) |
| N1i—N1—H1A | 121.5 | C3—C4—H4A | 120.5 |
| O2—N2—O3 | 123.8 (5) | C5—C4—H4A | 120.5 |
| O2—N2—C5 | 118.0 (5) | C4—C5—C6 | 120.8 (5) |
| O3—N2—C5 | 118.1 (5) | C4—C5—N2 | 119.1 (5) |
| O1—C1—N1 | 121.0 (4) | C6—C5—N2 | 119.8 (5) |
| O1—C1—C2 | 123.5 (4) | C7—C6—C5 | 119.9 (5) |
| N1—C1—C2 | 115.5 (4) | C7—C6—H6A | 120.0 |
| C7—C2—C3 | 118.6 (5) | C5—C6—H6A | 120.0 |
| C7—C2—C1 | 125.1 (5) | C6—C7—C2 | 120.6 (5) |
| C3—C2—C1 | 116.3 (5) | C6—C7—H7A | 119.7 |
| C4—C3—C2 | 120.9 (5) | C2—C7—H7A | 119.7 |
| C4—C3—H3A | 119.6 | ||
| N1i—N1—C1—O1 | 0.7 (8) | C3—C4—C5—N2 | −179.8 (5) |
| N1i—N1—C1—C2 | 179.0 (5) | O2—N2—C5—C4 | 10.3 (7) |
| O1—C1—C2—C7 | 148.0 (5) | O3—N2—C5—C4 | −166.2 (5) |
| N1—C1—C2—C7 | −30.3 (7) | O2—N2—C5—C6 | −164.5 (5) |
| O1—C1—C2—C3 | −31.9 (7) | O3—N2—C5—C6 | 19.0 (7) |
| N1—C1—C2—C3 | 149.8 (5) | C4—C5—C6—C7 | 5.5 (8) |
| C7—C2—C3—C4 | −3.0 (8) | N2—C5—C6—C7 | −179.8 (5) |
| C1—C2—C3—C4 | 176.9 (5) | C5—C6—C7—C2 | −4.6 (8) |
| C2—C3—C4—C5 | 3.8 (9) | C3—C2—C7—C6 | 3.4 (8) |
| C3—C4—C5—C6 | −5.0 (8) | C1—C2—C7—C6 | −176.5 (5) |
| Symmetry codes: (i) −x+2, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1ii | 0.86 | 2.12 | 2.881 (5) | 147 |
| Symmetry codes: (ii) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.86 | 2.12 | 2.881 (5) | 147 |
| Symmetry codes: (i) x+1, y, z. |
The authors acknowledge financial support by the Innovative and Entrepreneurial Project of Anhui Province for the Introduction of High-Level Talent (No. 2008Z038) and the Education Office of Anhui Province, China (No. KJ2007B227).
Cui, Z.-N., Wang, Z., Li, Y., Zhou, X.-Y., Ling, Y. & Yang, X.-L. (2007). Chin. J. Org. Chem. 27, 1300–1304.
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Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
Li, C.-M. & Ban, H.-Y. (2009). Acta Cryst. E65, o1466.
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Hydrazides have been demonstrated to possess excellent biological activities (Cui et al., 2007; Li & Ban, 2009). Recently a great deal of hydrazides have been synthesized and characterized (Shang et al., 2005a,b; Zhang et al., 2009; Li & Ban, 2009). We also are interested in this field of research, we report here the crystal structure of the title compound.
The molecular structure of the title compound has crystallographically imposed inversion symmetry located in the middle of the N—N bond (Fig. 1). One intermolecular hydrogen bond N—H···O is observed in the crystal structure (Table 1).