Acta Cryst. (2008). E64, o470 [ doi:10.1107/S1600536808001104 ]
The molecule of the title compound, C15H14N2O4, displays a trans configuration with respect to the hydrazide C=N bond. The dihedral angle between the two benzene rings is 15.0 (2)°. In the crystal structure, molecules are linked through intermolecular O-H
N and O-HO hydrogen bonds, forming layers parallel to the ab plane; an intramolecular N-HO hydrogen bond is also present.
4-Methoxybenzaldehyde (0.1 mmol, 13.6 mg) and 2,4-dihydroxybenzoic acid hydrazide (0.1 mmol, 16.8 mg) were dissolved in a 95% ethanol solution (10 ml). The mixture was stirred at room temperature to give a clear colourless solution. Crystals of the title compound were formed by gradual evaporation of the solvent over a period of three days at room temperature.
Atom H2A was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å. All other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with O—H = 0.82 Å, C—H = 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C, O) for methyl and hydroxy H atoms. In the absence of significant anomalous scattering effects, Friedel opposites were merged in the final refinement.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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]](./rz2192fig1thm.gif)
| Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 30% probability level. |
![[Figure 2]](./rz2192fig2thm.gif)
| Fig. 2. Crystal packing of the title compound viewed along the b axis. Intermolecular hydrogen bonds are shown as dashed lines. |
| C15H14N2O4 | F000 = 600 |
| Mr = 286.28 | Dx = 1.407 Mg m−3 |
| Orthorhombic, Pna21 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2c -2n | Cell parameters from 3064 reflections |
| a = 12.494 (3) Å | θ = 2.7–27.2º |
| b = 5.196 (1) Å | µ = 0.10 mm−1 |
| c = 20.825 (4) Å | T = 298 (2) K |
| V = 1351.9 (5) Å3 | Block, colourless |
| Z = 4 | 0.22 × 0.20 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 1519 independent reflections |
| Radiation source: fine-focus sealed tube | 1382 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.025 |
| T = 298(2) K | θmax = 27.0º |
| ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −15→15 |
| Tmin = 0.978, Tmax = 0.980 | k = −6→5 |
| 7661 measured reflections | l = −25→26 |
| 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)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0468P)2 + 0.123P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 1519 reflections | Δρmax = 0.13 e Å−3 |
| 196 parameters | Δρmin = −0.15 e Å−3 |
| 2 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| C15H14N2O4 | V = 1351.9 (5) Å3 |
| Mr = 286.28 | Z = 4 |
| Orthorhombic, Pna21 | Mo Kα |
| a = 12.494 (3) Å | µ = 0.10 mm−1 |
| b = 5.196 (1) Å | T = 298 (2) K |
| c = 20.825 (4) Å | 0.22 × 0.20 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 1519 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1382 reflections with I > 2σ(I) |
| Tmin = 0.978, Tmax = 0.980 | Rint = 0.025 |
| 7661 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.079 | Δρmax = 0.13 e Å−3 |
| S = 1.06 | Δρmin = −0.15 e Å−3 |
| 1519 reflections | Absolute structure: ? |
| 196 parameters | Flack parameter: ? |
| 2 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 | −0.07270 (13) | 0.0953 (3) | 0.95352 (10) | 0.0550 (5) | |
| O2 | 0.05579 (11) | 1.2801 (3) | 0.67387 (9) | 0.0461 (4) | |
| O3 | 0.37031 (11) | 1.3774 (3) | 0.73708 (8) | 0.0411 (4) | |
| H3 | 0.4359 | 1.3777 | 0.7357 | 0.062* | |
| O4 | 0.41377 (12) | 2.0606 (3) | 0.58664 (8) | 0.0438 (4) | |
| H4 | 0.4607 | 2.1038 | 0.6120 | 0.066* | |
| N1 | 0.11530 (13) | 0.9630 (3) | 0.76750 (9) | 0.0358 (4) | |
| N2 | 0.18526 (13) | 1.1298 (3) | 0.73763 (9) | 0.0354 (4) | |
| C1 | 0.09837 (17) | 0.6230 (4) | 0.84516 (11) | 0.0361 (4) | |
| C2 | −0.01216 (19) | 0.5952 (5) | 0.83938 (12) | 0.0461 (6) | |
| H2 | −0.0499 | 0.6974 | 0.8105 | 0.055* | |
| C3 | −0.06553 (18) | 0.4174 (5) | 0.87614 (13) | 0.0490 (6) | |
| H3A | −0.1392 | 0.3994 | 0.8717 | 0.059* | |
| C4 | −0.01114 (18) | 0.2637 (4) | 0.91993 (11) | 0.0394 (5) | |
| C5 | 0.09840 (18) | 0.2886 (4) | 0.92608 (12) | 0.0421 (5) | |
| H5 | 0.1360 | 0.1855 | 0.9548 | 0.051* | |
| C6 | 0.15162 (17) | 0.4694 (4) | 0.88882 (12) | 0.0424 (5) | |
| H6 | 0.2253 | 0.4876 | 0.8934 | 0.051* | |
| C7 | 0.15821 (17) | 0.8097 (4) | 0.80745 (11) | 0.0377 (5) | |
| H7 | 0.2320 | 0.8173 | 0.8129 | 0.045* | |
| C8 | 0.15001 (14) | 1.2894 (4) | 0.69171 (10) | 0.0317 (4) | |
| C9 | 0.22691 (14) | 1.4776 (4) | 0.66456 (10) | 0.0304 (4) | |
| C10 | 0.33078 (14) | 1.5226 (4) | 0.68779 (10) | 0.0306 (4) | |
| C11 | 0.39332 (15) | 1.7176 (4) | 0.66248 (10) | 0.0324 (4) | |
| H11 | 0.4610 | 1.7489 | 0.6793 | 0.039* | |
| C12 | 0.35562 (16) | 1.8657 (4) | 0.61231 (10) | 0.0335 (4) | |
| C13 | 0.25493 (16) | 1.8182 (4) | 0.58614 (11) | 0.0394 (5) | |
| H13 | 0.2303 | 1.9129 | 0.5512 | 0.047* | |
| C14 | 0.19282 (16) | 1.6282 (4) | 0.61303 (10) | 0.0373 (5) | |
| H14 | 0.1250 | 1.5987 | 0.5961 | 0.045* | |
| C15 | −0.0203 (2) | −0.0748 (5) | 0.99722 (14) | 0.0540 (6) | |
| H15A | 0.0135 | 0.0235 | 1.0306 | 0.081* | |
| H15B | 0.0328 | −0.1729 | 0.9746 | 0.081* | |
| H15C | −0.0720 | −0.1893 | 1.0159 | 0.081* | |
| H2A | 0.2547 (11) | 1.133 (6) | 0.7492 (17) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0502 (9) | 0.0531 (9) | 0.0618 (11) | −0.0010 (8) | 0.0024 (9) | 0.0263 (8) |
| O2 | 0.0247 (7) | 0.0480 (8) | 0.0657 (11) | −0.0043 (6) | −0.0063 (7) | 0.0119 (8) |
| O3 | 0.0221 (6) | 0.0521 (9) | 0.0490 (9) | −0.0013 (6) | −0.0039 (6) | 0.0161 (8) |
| O4 | 0.0398 (8) | 0.0458 (9) | 0.0458 (8) | −0.0114 (7) | −0.0038 (7) | 0.0110 (7) |
| N1 | 0.0311 (8) | 0.0368 (9) | 0.0395 (9) | −0.0081 (7) | 0.0034 (7) | 0.0004 (8) |
| N2 | 0.0258 (8) | 0.0401 (9) | 0.0404 (9) | −0.0046 (7) | 0.0007 (8) | 0.0049 (7) |
| C1 | 0.0364 (10) | 0.0354 (10) | 0.0364 (10) | −0.0019 (8) | −0.0005 (8) | −0.0012 (8) |
| C2 | 0.0383 (11) | 0.0517 (13) | 0.0481 (13) | −0.0061 (10) | −0.0100 (10) | 0.0175 (11) |
| C3 | 0.0346 (10) | 0.0557 (13) | 0.0567 (14) | −0.0070 (10) | −0.0084 (11) | 0.0186 (11) |
| C4 | 0.0422 (12) | 0.0360 (10) | 0.0399 (11) | −0.0009 (9) | 0.0012 (9) | 0.0062 (9) |
| C5 | 0.0439 (12) | 0.0400 (11) | 0.0425 (11) | 0.0066 (9) | −0.0042 (9) | 0.0068 (10) |
| C6 | 0.0347 (10) | 0.0451 (12) | 0.0476 (13) | 0.0029 (9) | −0.0033 (10) | 0.0006 (10) |
| C7 | 0.0311 (10) | 0.0418 (11) | 0.0404 (11) | −0.0033 (9) | −0.0001 (9) | −0.0023 (9) |
| C8 | 0.0239 (9) | 0.0318 (9) | 0.0394 (10) | 0.0013 (7) | 0.0020 (8) | −0.0037 (8) |
| C9 | 0.0233 (8) | 0.0324 (9) | 0.0356 (10) | 0.0009 (7) | 0.0000 (8) | −0.0020 (8) |
| C10 | 0.0240 (8) | 0.0333 (9) | 0.0346 (10) | 0.0032 (7) | 0.0006 (8) | 0.0007 (8) |
| C11 | 0.0227 (8) | 0.0371 (10) | 0.0376 (10) | −0.0001 (7) | −0.0016 (8) | −0.0006 (8) |
| C12 | 0.0296 (9) | 0.0346 (10) | 0.0363 (10) | −0.0020 (8) | 0.0024 (8) | −0.0004 (8) |
| C13 | 0.0333 (10) | 0.0460 (11) | 0.0389 (11) | −0.0003 (9) | −0.0065 (9) | 0.0089 (10) |
| C14 | 0.0262 (9) | 0.0437 (11) | 0.0419 (11) | −0.0031 (8) | −0.0081 (8) | 0.0019 (9) |
| C15 | 0.0663 (16) | 0.0453 (12) | 0.0504 (14) | 0.0093 (13) | 0.0052 (13) | 0.0159 (11) |
| O1—C4 | 1.359 (3) | C4—C5 | 1.381 (3) |
| O1—C15 | 1.427 (3) | C5—C6 | 1.388 (3) |
| O2—C8 | 1.235 (2) | C5—H5 | 0.9300 |
| O3—C10 | 1.366 (2) | C6—H6 | 0.9300 |
| O3—H3 | 0.8200 | C7—H7 | 0.9300 |
| O4—C12 | 1.356 (2) | C8—C9 | 1.483 (3) |
| O4—H4 | 0.8200 | C9—C14 | 1.394 (3) |
| N1—C7 | 1.270 (3) | C9—C10 | 1.405 (3) |
| N1—N2 | 1.379 (2) | C10—C11 | 1.384 (3) |
| N2—C8 | 1.340 (3) | C11—C12 | 1.380 (3) |
| N2—H2A | 0.901 (10) | C11—H11 | 0.9300 |
| C1—C6 | 1.381 (3) | C12—C13 | 1.393 (3) |
| C1—C2 | 1.394 (3) | C13—C14 | 1.375 (3) |
| C1—C7 | 1.455 (3) | C13—H13 | 0.9300 |
| C2—C3 | 1.373 (3) | C14—H14 | 0.9300 |
| C2—H2 | 0.9300 | C15—H15A | 0.9600 |
| C3—C4 | 1.390 (3) | C15—H15B | 0.9600 |
| C3—H3A | 0.9300 | C15—H15C | 0.9600 |
| C4—O1—C15 | 117.86 (19) | O2—C8—N2 | 120.23 (18) |
| C10—O3—H3 | 109.5 | O2—C8—C9 | 121.91 (18) |
| C12—O4—H4 | 109.5 | N2—C8—C9 | 117.85 (16) |
| C7—N1—N2 | 114.96 (16) | C14—C9—C10 | 117.00 (17) |
| C8—N2—N1 | 120.15 (16) | C14—C9—C8 | 117.74 (17) |
| C8—N2—H2A | 120 (2) | C10—C9—C8 | 125.23 (17) |
| N1—N2—H2A | 120 (2) | O3—C10—C11 | 119.10 (16) |
| C6—C1—C2 | 118.3 (2) | O3—C10—C9 | 120.06 (16) |
| C6—C1—C7 | 119.57 (19) | C11—C10—C9 | 120.82 (17) |
| C2—C1—C7 | 122.1 (2) | C12—C11—C10 | 120.26 (17) |
| C3—C2—C1 | 120.2 (2) | C12—C11—H11 | 119.9 |
| C3—C2—H2 | 119.9 | C10—C11—H11 | 119.9 |
| C1—C2—H2 | 119.9 | O4—C12—C11 | 122.14 (18) |
| C2—C3—C4 | 121.0 (2) | O4—C12—C13 | 117.50 (18) |
| C2—C3—H3A | 119.5 | C11—C12—C13 | 120.36 (18) |
| C4—C3—H3A | 119.5 | C14—C13—C12 | 118.52 (19) |
| O1—C4—C5 | 125.0 (2) | C14—C13—H13 | 120.7 |
| O1—C4—C3 | 115.5 (2) | C12—C13—H13 | 120.7 |
| C5—C4—C3 | 119.5 (2) | C13—C14—C9 | 122.94 (18) |
| C4—C5—C6 | 119.1 (2) | C13—C14—H14 | 118.5 |
| C4—C5—H5 | 120.4 | C9—C14—H14 | 118.5 |
| C6—C5—H5 | 120.4 | O1—C15—H15A | 109.5 |
| C1—C6—C5 | 121.9 (2) | O1—C15—H15B | 109.5 |
| C1—C6—H6 | 119.0 | H15A—C15—H15B | 109.5 |
| C5—C6—H6 | 119.0 | O1—C15—H15C | 109.5 |
| N1—C7—C1 | 123.69 (19) | H15A—C15—H15C | 109.5 |
| N1—C7—H7 | 118.2 | H15B—C15—H15C | 109.5 |
| C1—C7—H7 | 118.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O3 | 0.901 (10) | 1.94 (2) | 2.646 (2) | 134 (3) |
| O4—H4···O2i | 0.82 | 1.85 | 2.671 (2) | 174 |
| O3—H3···N1ii | 0.82 | 2.48 | 3.234 (2) | 154 |
| O3—H3···O2ii | 0.82 | 2.14 | 2.788 (2) | 136 |
| Symmetry codes: (i) x+1/2, −y+7/2, z; (ii) x+1/2, −y+5/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O3 | 0.901 (10) | 1.94 (2) | 2.646 (2) | 134 (3) |
| O4—H4···O2i | 0.82 | 1.85 | 2.671 (2) | 174 |
| O3—H3···N1ii | 0.82 | 2.48 | 3.234 (2) | 154 |
| O3—H3···O2ii | 0.82 | 2.14 | 2.788 (2) | 136 |
| Symmetry codes: (i) x+1/2, −y+7/2, z; (ii) x+1/2, −y+5/2, z. |
This project was supported by a research grant from the Dalian Medical University.
Brückner, C., Rettig, S. J. & Dolphin, D. (2000). Inorg. Chem. 39, 6100–6106.
Bruker (2000). SMART (Version 5.625), SAINT (Version 6.01). and SADABS (Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
Diao, Y.-P. (2007). Acta Cryst. E63, m1453–m1454.
Diao, Y.-P., Shu, X.-H., Zhang, B.-J., Zhen, Y.-H. & Kang, T.-G. (2007). Acta Cryst. E63, m1816–?.
Harrop, T. C., Olmstead, M. M. & Mascharak, P. K. (2003). Chem. Commun. pp. 410–411.
Huang, S.-S., Zhou, Q. & Diao, Y.-P. (2007). Acta Cryst. E63, o4659–?.
Li, K., Huang, S.-S., Zhang, B.-J., Meng, D.-L. & Diao, Y.-P. (2007). Acta Cryst. E63, m2291–?.
Ren, S., Wang, R., Komatsu, K., Bonaz-Krause, P., Zyrianov, Y., McKenna, C. E., Csipke, C., Tokes, Z. A. & Lien, E. J. (2002). J. Med. Chem. 45, 410–419.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Schiff base compounds have received much attention in recent years. Some Schiff base metal complexes have been found to have pharmacological and antitumor properties (Brückner et al., 2000; Harrop et al., 2003; Ren et al., 2002). As part of our research programme on the synthesis and characterization of Schiff base compounds (Diao et al., 2007; Diao, 2007; Li et al., 2007; Huang et al., 2007), we report here the structure of the title ligand.
The molecule of the title compound displays a trans configuration with respect to the C=N bond (Fig. 1). The dihedral angle between the two benzene rings is 15.0 (2)°. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen interaction (Table 1). In the crystal, molecules are linked through intermolecular O—H···N and O—H···O hydrogen bonds (Table 1), forming layers parallel to the ab plane (Fig. 2).