Acta Cryst. (2009). E65, o1466 [ doi:10.1107/S1600536809020066 ]
The molecule of the title compound, C14H11N3O4, is approximately planar, the dihedral angle between the planes of the two substituted benzene rings being 2.54 (7)°. The molecule exists in a trans configuration with respect to the central methylidene unit. In the crystal structure, molecules are linked through intermolecular O-H
O, N-HO and C-HO hydrogen bonds, forming layers parallel to (101). The O/N-HO and C-HO interactions form a pair of bifurcated acceptor bonds involving the cabonyl/nitro O atom, generating an R21(6) motif.
The title compound was prepared by refluxing 4-nitrobenzaldehyde (1.0 mol) with 4-hydroxybenzohydrazide (1.0 mol) in methanol (100 ml). Excess methanol was removed from the mixture by distillation. A colourless solid product was filtered, and washed three times with methanol. Colourless block-shaped crystals of the title compound were obtained from a methanol solution by slow evaporation in air.
Atom H2B was located in a difference Fourier map and refined isotropically, with the N–H distance restrained to 0.90 (1)Å and Uiso fixed at 0.08 Å2. The remaining H atoms were placed in calculated positions (C–H = 0.93 Å and O–H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ci2812fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for the non-hydrogen atoms. |
![[Figure 2]](./ci2812fig2thm.gif)
| Fig. 2. The packing diagram of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines. |
| C14H11N3O4 | F(000) = 592 |
| Mr = 285.26 | Dx = 1.451 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2390 reflections |
| a = 7.659 (1) Å | θ = 3.0–30.5° |
| b = 13.587 (2) Å | µ = 0.11 mm−1 |
| c = 12.561 (2) Å | T = 298 K |
| β = 92.784 (5)° | Block, colourless |
| V = 1305.6 (3) Å3 | 0.20 × 0.20 × 0.18 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2835 independent reflections |
| Radiation source: fine-focus sealed tube | 2109 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| ω scans | θmax = 27.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
| Tmin = 0.979, Tmax = 0.981 | k = −17→15 |
| 7862 measured reflections | l = −15→15 |
| 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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.3196P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 2835 reflections | Δρmax = 0.21 e Å−3 |
| 195 parameters | Δρmin = −0.13 e Å−3 |
| 1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0104 (15) |
| C14H11N3O4 | V = 1305.6 (3) Å3 |
| Mr = 285.26 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 7.659 (1) Å | µ = 0.11 mm−1 |
| b = 13.587 (2) Å | T = 298 K |
| c = 12.561 (2) Å | 0.20 × 0.20 × 0.18 mm |
| β = 92.784 (5)° |
| Bruker SMART CCD area-detector diffractometer | 2835 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2109 reflections with I > 2σ(I) |
| Tmin = 0.979, Tmax = 0.981 | Rint = 0.027 |
| 7862 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.111 | Δρmax = 0.21 e Å−3 |
| S = 1.03 | Δρmin = −0.13 e Å−3 |
| 2835 reflections | Absolute structure: ? |
| 195 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
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 > 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 | ||
| N1 | 0.20673 (17) | 0.97706 (9) | 1.04460 (10) | 0.0410 (3) | |
| N2 | 0.26363 (19) | 1.05171 (9) | 0.98149 (10) | 0.0431 (3) | |
| N3 | 0.0157 (2) | 0.54652 (10) | 1.21921 (11) | 0.0504 (4) | |
| O1 | 0.18428 (15) | 1.16731 (8) | 1.09824 (8) | 0.0472 (3) | |
| O2 | 0.51173 (18) | 1.44263 (8) | 0.75115 (9) | 0.0541 (3) | |
| H2 | 0.5548 | 1.4194 | 0.6982 | 0.081* | |
| O3 | 0.0321 (2) | 0.46801 (10) | 1.17422 (12) | 0.0883 (6) | |
| O4 | −0.04623 (18) | 0.55386 (9) | 1.30667 (10) | 0.0611 (4) | |
| C1 | 0.1672 (2) | 0.80400 (11) | 1.06387 (12) | 0.0391 (4) | |
| C2 | 0.1011 (2) | 0.80979 (11) | 1.16524 (12) | 0.0423 (4) | |
| H2A | 0.0898 | 0.8707 | 1.1980 | 0.051* | |
| C3 | 0.0527 (2) | 0.72557 (12) | 1.21665 (12) | 0.0418 (4) | |
| H3 | 0.0085 | 0.7288 | 1.2842 | 0.050* | |
| C4 | 0.0707 (2) | 0.63608 (11) | 1.16619 (12) | 0.0402 (4) | |
| C5 | 0.1366 (2) | 0.62796 (12) | 1.06648 (13) | 0.0455 (4) | |
| H5 | 0.1483 | 0.5668 | 1.0344 | 0.055* | |
| C6 | 0.1845 (2) | 0.71259 (12) | 1.01580 (12) | 0.0450 (4) | |
| H6 | 0.2290 | 0.7087 | 0.9484 | 0.054* | |
| C7 | 0.2198 (2) | 0.89103 (11) | 1.00586 (13) | 0.0439 (4) | |
| H7 | 0.2642 | 0.8835 | 0.9387 | 0.053* | |
| C8 | 0.25098 (19) | 1.14649 (11) | 1.01458 (11) | 0.0354 (3) | |
| C9 | 0.32220 (19) | 1.22217 (11) | 0.94326 (11) | 0.0348 (3) | |
| C10 | 0.3187 (2) | 1.32057 (11) | 0.97329 (12) | 0.0404 (4) | |
| H10 | 0.2734 | 1.3378 | 1.0381 | 0.048* | |
| C11 | 0.3812 (2) | 1.39297 (11) | 0.90850 (13) | 0.0447 (4) | |
| H11 | 0.3772 | 1.4585 | 0.9298 | 0.054* | |
| C12 | 0.4503 (2) | 1.36889 (11) | 0.81144 (12) | 0.0390 (4) | |
| C13 | 0.4543 (2) | 1.27096 (11) | 0.78040 (12) | 0.0410 (4) | |
| H13 | 0.4995 | 1.2538 | 0.7156 | 0.049* | |
| C14 | 0.3915 (2) | 1.19946 (11) | 0.84559 (12) | 0.0403 (4) | |
| H14 | 0.3952 | 1.1340 | 0.8240 | 0.048* | |
| H2B | 0.303 (3) | 1.0358 (15) | 0.9176 (10) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0486 (8) | 0.0377 (7) | 0.0377 (7) | −0.0014 (6) | 0.0127 (6) | 0.0081 (6) |
| N2 | 0.0616 (9) | 0.0335 (7) | 0.0359 (7) | −0.0021 (6) | 0.0200 (6) | 0.0028 (5) |
| N3 | 0.0650 (10) | 0.0397 (8) | 0.0477 (8) | −0.0055 (7) | 0.0146 (7) | 0.0081 (6) |
| O1 | 0.0630 (7) | 0.0441 (6) | 0.0364 (6) | 0.0005 (5) | 0.0217 (5) | −0.0009 (5) |
| O2 | 0.0760 (9) | 0.0361 (6) | 0.0525 (7) | −0.0056 (6) | 0.0280 (6) | 0.0047 (5) |
| O3 | 0.1579 (16) | 0.0359 (7) | 0.0749 (10) | −0.0156 (9) | 0.0465 (10) | −0.0013 (7) |
| O4 | 0.0814 (9) | 0.0505 (7) | 0.0537 (7) | −0.0059 (6) | 0.0289 (7) | 0.0118 (6) |
| C1 | 0.0401 (8) | 0.0381 (8) | 0.0395 (8) | −0.0015 (6) | 0.0068 (6) | 0.0070 (6) |
| C2 | 0.0511 (10) | 0.0350 (8) | 0.0413 (9) | −0.0008 (7) | 0.0087 (7) | 0.0012 (6) |
| C3 | 0.0477 (9) | 0.0425 (9) | 0.0358 (8) | 0.0001 (7) | 0.0103 (7) | 0.0051 (7) |
| C4 | 0.0440 (9) | 0.0364 (8) | 0.0408 (8) | −0.0029 (7) | 0.0073 (7) | 0.0076 (6) |
| C5 | 0.0563 (10) | 0.0368 (8) | 0.0446 (9) | −0.0019 (7) | 0.0129 (8) | 0.0002 (7) |
| C6 | 0.0546 (10) | 0.0436 (9) | 0.0379 (8) | −0.0008 (7) | 0.0141 (7) | 0.0029 (7) |
| C7 | 0.0526 (10) | 0.0418 (9) | 0.0384 (8) | −0.0023 (7) | 0.0135 (7) | 0.0047 (7) |
| C8 | 0.0375 (8) | 0.0388 (8) | 0.0307 (7) | 0.0026 (6) | 0.0091 (6) | 0.0001 (6) |
| C9 | 0.0378 (8) | 0.0342 (7) | 0.0331 (7) | 0.0017 (6) | 0.0095 (6) | −0.0003 (6) |
| C10 | 0.0495 (9) | 0.0379 (8) | 0.0352 (8) | 0.0012 (7) | 0.0158 (7) | −0.0050 (6) |
| C11 | 0.0568 (10) | 0.0313 (8) | 0.0473 (9) | −0.0003 (7) | 0.0161 (7) | −0.0051 (7) |
| C12 | 0.0432 (9) | 0.0333 (7) | 0.0414 (8) | −0.0014 (6) | 0.0111 (7) | 0.0027 (6) |
| C13 | 0.0516 (9) | 0.0385 (8) | 0.0345 (8) | −0.0003 (7) | 0.0178 (7) | −0.0022 (6) |
| C14 | 0.0529 (9) | 0.0302 (7) | 0.0394 (8) | −0.0006 (6) | 0.0165 (7) | −0.0034 (6) |
| N1—C7 | 1.272 (2) | C4—C5 | 1.377 (2) |
| N1—N2 | 1.3714 (17) | C5—C6 | 1.373 (2) |
| N2—C8 | 1.3581 (19) | C5—H5 | 0.93 |
| N2—H2B | 0.899 (9) | C6—H6 | 0.93 |
| N3—O3 | 1.2164 (18) | C7—H7 | 0.93 |
| N3—O4 | 1.2219 (17) | C8—C9 | 1.4848 (19) |
| N3—C4 | 1.4590 (19) | C9—C10 | 1.390 (2) |
| O1—C8 | 1.2237 (16) | C9—C14 | 1.395 (2) |
| O2—C12 | 1.3539 (17) | C10—C11 | 1.377 (2) |
| O2—H2 | 0.82 | C10—H10 | 0.93 |
| C1—C6 | 1.390 (2) | C11—C12 | 1.392 (2) |
| C1—C2 | 1.395 (2) | C11—H11 | 0.93 |
| C1—C7 | 1.456 (2) | C12—C13 | 1.387 (2) |
| C2—C3 | 1.374 (2) | C13—C14 | 1.373 (2) |
| C2—H2A | 0.93 | C13—H13 | 0.93 |
| C3—C4 | 1.381 (2) | C14—H14 | 0.93 |
| C3—H3 | 0.93 | ||
| C7—N1—N2 | 115.18 (12) | C1—C6—H6 | 119.5 |
| C8—N2—N1 | 119.67 (12) | N1—C7—C1 | 121.73 (14) |
| C8—N2—H2B | 122.3 (14) | N1—C7—H7 | 119.1 |
| N1—N2—H2B | 117.9 (14) | C1—C7—H7 | 119.1 |
| O3—N3—O4 | 122.86 (14) | O1—C8—N2 | 121.40 (13) |
| O3—N3—C4 | 118.74 (14) | O1—C8—C9 | 122.61 (13) |
| O4—N3—C4 | 118.40 (14) | N2—C8—C9 | 115.99 (12) |
| C12—O2—H2 | 109.5 | C10—C9—C14 | 117.70 (13) |
| C6—C1—C2 | 119.55 (14) | C10—C9—C8 | 119.34 (13) |
| C6—C1—C7 | 118.28 (14) | C14—C9—C8 | 122.96 (13) |
| C2—C1—C7 | 122.18 (14) | C11—C10—C9 | 120.99 (14) |
| C3—C2—C1 | 120.02 (14) | C11—C10—H10 | 119.5 |
| C3—C2—H2A | 120.0 | C9—C10—H10 | 119.5 |
| C1—C2—H2A | 120.0 | C10—C11—C12 | 120.51 (14) |
| C2—C3—C4 | 118.84 (14) | C10—C11—H11 | 119.7 |
| C2—C3—H3 | 120.6 | C12—C11—H11 | 119.7 |
| C4—C3—H3 | 120.6 | O2—C12—C13 | 122.66 (13) |
| C5—C4—C3 | 122.48 (14) | O2—C12—C11 | 118.25 (13) |
| C5—C4—N3 | 118.35 (14) | C13—C12—C11 | 119.09 (14) |
| C3—C4—N3 | 119.16 (13) | C14—C13—C12 | 119.87 (13) |
| C6—C5—C4 | 118.20 (15) | C14—C13—H13 | 120.1 |
| C6—C5—H5 | 120.9 | C12—C13—H13 | 120.1 |
| C4—C5—H5 | 120.9 | C13—C14—C9 | 121.84 (14) |
| C5—C6—C1 | 120.91 (14) | C13—C14—H14 | 119.1 |
| C5—C6—H6 | 119.5 | C9—C14—H14 | 119.1 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 2.02 | 2.8131 (15) | 164 |
| N2—H2B···O4ii | 0.90 (1) | 2.22 (1) | 3.0513 (17) | 155 (2) |
| C7—H7···O4ii | 0.93 | 2.41 | 3.235 (2) | 148 |
| C13—H13···O1i | 0.93 | 2.35 | 3.0713 (19) | 134 |
| Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 2.02 | 2.8131 (15) | 164 |
| N2—H2B···O4ii | 0.90 (1) | 2.22 (1) | 3.0513 (17) | 155 (2) |
| C7—H7···O4ii | 0.93 | 2.41 | 3.235 (2) | 148 |
| C13—H13···O1i | 0.93 | 2.35 | 3.0713 (19) | 134 |
| Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2. |
The authors acknowledge financial support by the Research Foundation of Liaoning Province (grant No. 2008470).
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Schiff bases derived from the condensation of aldehydes with hydrazides have been demonstrated to possess excellent biological activities (Zhong et al., 2007; Raj et al., 2007; Jimenez-Pulido et al., 2008). Due to the easy synthesis of such compounds, a great deal of Schiff bases have been synthesized and structurally characterized (Yehye et al., 2008; Fun et al., 2008a,b; Yang et al., 2008; Ejsmont et al., 2008). Recently, we have reported a few such compounds (Ban & Li, 2008a,b; Li & Ban, 2009a,b). We report here the crystal structure of the title new compound.
The title Schiff base molecule (Fig. 1) is nearly planar, with the dihedral angle between the two benzene rings being 2.54 (7)°. The molecule exists in a trans configuration with respect to the central methylidene (C7═N1) unit. The N2—N1—C7—C1 torsion angle is 179.12 (14)°.
In the crystal structure, the molecules are linked through intermolecular O—H···O and N—H···O hydrogen bonds (Table 1), forming layers parallel to the (101) (Fig. 2). Within the layer, C—H···O hydrogen bonds are also observed.