Acta Cryst. (2009). E65, o2097 [ doi:10.1107/S1600536809030712 ]
In the title compound, C9H10N2O3, the Schiff base molecule is approximately planar, the dihedral angle between the benzene ring and the acetohydrazide group (r.m.s. deviation = 0.034 Å) being 8.81 (7)°. An intramolecular O-H
O hydrogen bond is observed. In the crystal, molecules are linked into a three-dimensional network by O-HO, N-HO and C-HO hydrogen bonds.
3,4-Dihydroxybenzaldehyde (1.38 g, 0.01 mol) and acetohydrazide (0.74 g, 0.01 mol) were dissolved in stirred methanol (20 ml) and left for 2.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 85% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 475–477 K).
H atoms were positioned geometrically (N-H = 0.86 Å, O-H = 0.82Å and C-H = 0.93 or 0.96Å) and refined using a riding model, with Uiso(H) =1.2Ueq(C,N) and 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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]](./ci2878fig1thm.gif)
| Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level. The dashed line indicates a hydrogen bond. |
![[Figure 2]](./ci2878fig2thm.gif)
| Fig. 2. Part of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines. |
| C9H10N2O3 | F(000) = 408 |
| Mr = 194.19 | Dx = 1.411 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2066 reflections |
| a = 10.598 (2) Å | θ = 2.0–27.4° |
| b = 8.5017 (16) Å | µ = 0.11 mm−1 |
| c = 10.621 (2) Å | T = 223 K |
| β = 107.232 (7)° | Block, colourless |
| V = 913.9 (3) Å3 | 0.25 × 0.24 × 0.20 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2066 independent reflections |
| Radiation source: fine-focus sealed tube | 1665 reflections with I > 2σ(I) |
| graphite | Rint = 0.023 |
| φ and ω scans | θmax = 27.4°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −13→13 |
| Tmin = 0.972, Tmax = 0.980 | k = −10→10 |
| 5752 measured reflections | l = −13→12 |
| 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)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0674P)2 + 0.2108P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.94 | (Δ/σ)max = 0.009 |
| 2066 reflections | Δρmax = 0.21 e Å−3 |
| 129 parameters | Δρmin = −0.17 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.019 (4) |
| C9H10N2O3 | V = 913.9 (3) Å3 |
| Mr = 194.19 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.598 (2) Å | µ = 0.11 mm−1 |
| b = 8.5017 (16) Å | T = 223 K |
| c = 10.621 (2) Å | 0.25 × 0.24 × 0.20 mm |
| β = 107.232 (7)° |
| Bruker SMART CCD area-detector diffractometer | 2066 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1665 reflections with I > 2σ(I) |
| Tmin = 0.972, Tmax = 0.980 | Rint = 0.023 |
| 5752 measured reflections | θmax = 27.4° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.111 | Δρmax = 0.21 e Å−3 |
| S = 0.94 | Δρmin = −0.17 e Å−3 |
| 2066 reflections | Absolute structure: ? |
| 129 parameters | Flack parameter: ? |
| 0 restraints | 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 | ||
| N2 | 1.00361 (10) | 0.13127 (13) | 0.68707 (10) | 0.0357 (3) | |
| H2 | 0.9880 | 0.0352 | 0.7029 | 0.043* | |
| O3 | 0.47733 (10) | 0.25734 (12) | 0.01091 (10) | 0.0522 (3) | |
| H3 | 0.4848 | 0.3492 | −0.0093 | 0.078* | |
| O2 | 0.64301 (9) | 0.48688 (11) | 0.14025 (10) | 0.0424 (3) | |
| H2A | 0.6973 | 0.5473 | 0.1870 | 0.064* | |
| O1 | 1.13124 (9) | 0.34588 (11) | 0.75557 (10) | 0.0445 (3) | |
| N1 | 0.93041 (10) | 0.20010 (13) | 0.56882 (11) | 0.0362 (3) | |
| C6 | 0.75370 (12) | 0.15246 (15) | 0.36828 (13) | 0.0345 (3) | |
| C3 | 0.56800 (13) | 0.22557 (16) | 0.12889 (13) | 0.0374 (3) | |
| C1 | 0.74814 (12) | 0.30536 (15) | 0.31694 (13) | 0.0338 (3) | |
| H1 | 0.8063 | 0.3821 | 0.3628 | 0.041* | |
| C2 | 0.65615 (12) | 0.34155 (15) | 0.19818 (12) | 0.0333 (3) | |
| C5 | 0.66449 (13) | 0.03947 (16) | 0.29930 (14) | 0.0397 (3) | |
| H5 | 0.6673 | −0.0617 | 0.3334 | 0.048* | |
| C8 | 1.09751 (12) | 0.21065 (15) | 0.77666 (13) | 0.0336 (3) | |
| C9 | 1.15560 (15) | 0.12587 (18) | 0.90450 (13) | 0.0440 (3) | |
| H9A | 1.1378 | 0.0153 | 0.8919 | 0.066* | |
| H9B | 1.1169 | 0.1653 | 0.9693 | 0.066* | |
| H9C | 1.2494 | 0.1427 | 0.9342 | 0.066* | |
| C7 | 0.84748 (13) | 0.10590 (15) | 0.49377 (13) | 0.0359 (3) | |
| H7 | 0.8468 | 0.0018 | 0.5205 | 0.043* | |
| C4 | 0.57178 (14) | 0.07602 (16) | 0.18054 (14) | 0.0412 (3) | |
| H4 | 0.5122 | 0.0000 | 0.1357 | 0.049* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N2 | 0.0383 (6) | 0.0271 (6) | 0.0362 (6) | −0.0028 (4) | 0.0024 (5) | 0.0041 (4) |
| O3 | 0.0513 (6) | 0.0409 (6) | 0.0465 (6) | −0.0082 (4) | −0.0132 (5) | 0.0037 (4) |
| O2 | 0.0409 (5) | 0.0333 (5) | 0.0426 (6) | −0.0053 (4) | −0.0036 (4) | 0.0054 (4) |
| O1 | 0.0454 (5) | 0.0301 (5) | 0.0501 (6) | −0.0069 (4) | 0.0019 (4) | 0.0001 (4) |
| N1 | 0.0360 (6) | 0.0332 (6) | 0.0354 (6) | 0.0007 (4) | 0.0045 (5) | 0.0048 (4) |
| C6 | 0.0347 (6) | 0.0349 (7) | 0.0326 (7) | −0.0013 (5) | 0.0081 (5) | 0.0000 (5) |
| C3 | 0.0341 (7) | 0.0385 (7) | 0.0347 (7) | −0.0021 (5) | 0.0024 (5) | −0.0019 (5) |
| C1 | 0.0322 (6) | 0.0320 (7) | 0.0345 (7) | −0.0046 (5) | 0.0060 (5) | −0.0027 (5) |
| C2 | 0.0326 (6) | 0.0304 (6) | 0.0350 (7) | −0.0018 (5) | 0.0070 (5) | −0.0001 (5) |
| C5 | 0.0436 (7) | 0.0323 (7) | 0.0402 (7) | −0.0048 (5) | 0.0079 (6) | 0.0020 (5) |
| C8 | 0.0332 (6) | 0.0288 (6) | 0.0376 (7) | 0.0014 (5) | 0.0086 (5) | −0.0027 (5) |
| C9 | 0.0470 (8) | 0.0416 (8) | 0.0376 (8) | 0.0004 (6) | 0.0038 (6) | 0.0022 (6) |
| C7 | 0.0384 (7) | 0.0315 (7) | 0.0363 (7) | −0.0022 (5) | 0.0087 (5) | 0.0024 (5) |
| C4 | 0.0406 (7) | 0.0355 (7) | 0.0416 (8) | −0.0097 (5) | 0.0031 (6) | −0.0047 (6) |
| N2—C8 | 1.3380 (16) | C3—C4 | 1.381 (2) |
| N2—N1 | 1.3944 (14) | C3—C2 | 1.4069 (18) |
| N2—H2 | 0.86 | C1—C2 | 1.3811 (18) |
| O3—C3 | 1.3612 (16) | C1—H1 | 0.93 |
| O3—H3 | 0.82 | C5—C4 | 1.3851 (19) |
| O2—C2 | 1.3689 (16) | C5—H5 | 0.93 |
| O2—H2A | 0.82 | C8—C9 | 1.4989 (19) |
| O1—C8 | 1.2438 (16) | C9—H9A | 0.96 |
| N1—C7 | 1.2783 (17) | C9—H9B | 0.96 |
| C6—C5 | 1.3939 (18) | C9—H9C | 0.96 |
| C6—C1 | 1.4041 (18) | C7—H7 | 0.93 |
| C6—C7 | 1.4615 (18) | C4—H4 | 0.93 |
| C8—N2—N1 | 121.80 (11) | C4—C5—C6 | 120.78 (13) |
| C8—N2—H2 | 119.1 | C4—C5—H5 | 119.6 |
| N1—N2—H2 | 119.1 | C6—C5—H5 | 119.6 |
| C3—O3—H3 | 109.5 | O1—C8—N2 | 122.07 (12) |
| C2—O2—H2A | 109.5 | O1—C8—C9 | 123.01 (12) |
| C7—N1—N2 | 113.26 (11) | N2—C8—C9 | 114.90 (12) |
| C5—C6—C1 | 119.34 (12) | C8—C9—H9A | 109.5 |
| C5—C6—C7 | 117.70 (12) | C8—C9—H9B | 109.5 |
| C1—C6—C7 | 122.94 (12) | H9A—C9—H9B | 109.5 |
| O3—C3—C4 | 118.55 (12) | C8—C9—H9C | 109.5 |
| O3—C3—C2 | 121.38 (12) | H9A—C9—H9C | 109.5 |
| C4—C3—C2 | 120.06 (12) | H9B—C9—H9C | 109.5 |
| C2—C1—C6 | 119.86 (12) | N1—C7—C6 | 123.72 (12) |
| C2—C1—H1 | 120.1 | N1—C7—H7 | 118.1 |
| C6—C1—H1 | 120.1 | C6—C7—H7 | 118.1 |
| O2—C2—C1 | 124.19 (11) | C3—C4—C5 | 119.85 (12) |
| O2—C2—C3 | 115.73 (11) | C3—C4—H4 | 120.1 |
| C1—C2—C3 | 120.09 (12) | C5—C4—H4 | 120.1 |
| C8—N2—N1—C7 | 178.32 (12) | C7—C6—C5—C4 | 179.18 (13) |
| C5—C6—C1—C2 | −0.99 (19) | N1—N2—C8—O1 | −5.29 (19) |
| C7—C6—C1—C2 | −179.44 (12) | N1—N2—C8—C9 | 173.18 (11) |
| C6—C1—C2—O2 | 179.96 (12) | N2—N1—C7—C6 | 176.10 (11) |
| C6—C1—C2—C3 | 0.13 (19) | C5—C6—C7—N1 | −176.99 (13) |
| O3—C3—C2—O2 | 0.93 (19) | C1—C6—C7—N1 | 1.5 (2) |
| C4—C3—C2—O2 | −178.75 (12) | O3—C3—C4—C5 | 178.87 (13) |
| O3—C3—C2—C1 | −179.22 (12) | C2—C3—C4—C5 | −1.4 (2) |
| C4—C3—C2—C1 | 1.1 (2) | C6—C5—C4—C3 | 0.6 (2) |
| C1—C6—C5—C4 | 0.7 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.86 | 2.17 | 2.9692 (15) | 154 |
| O2—H2A···O1ii | 0.82 | 1.96 | 2.7206 (13) | 154 |
| O3—H3···O2 | 0.82 | 2.26 | 2.7109 (14) | 115 |
| O3—H3···O2iii | 0.82 | 2.14 | 2.7784 (14) | 134 |
| C9—H9C···O3iv | 0.96 | 2.51 | 3.445 (2) | 166 |
| Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x+1, y, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.86 | 2.17 | 2.9692 (15) | 154 |
| O2—H2A···O1ii | 0.82 | 1.96 | 2.7206 (13) | 154 |
| O3—H3···O2 | 0.82 | 2.26 | 2.7109 (14) | 115 |
| O3—H3···O2iii | 0.82 | 2.14 | 2.7784 (14) | 134 |
| C9—H9C···O3iv | 0.96 | 2.51 | 3.445 (2) | 166 |
| Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x+1, y, z+1. |
The authors thank the Science and Technology Project of Zhejiang Province (grant No. 2007 F70077) for financial support.
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Richardson, D., Baker, E., Ponka, P., Wilairat, P., Vitolo, M. L. & Webb, J. (1988). Thalassemia: Pathophysiology and Management, Part B. p. 81. New York: Alan R. Liss Inc.
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Tamboura, F. B., Gaye, M., Sall, A. S., Barry, A. H. & Bah, Y. (2009). Acta Cryst. E65, m160–m161.
Schiff bases have attracted much attention due to the possibility of their analytical applications (Cimerman et al., 1997). They are also important ligands, which have been reported to have mild bacteriostatic activity and as potential oral iron-chelating drugs for genetic disorders such as thalassemia (Offe et al., 1952; Richardson et al., 1988). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various complexes (Tamboura et al., 2009). We report here the crystal structure of the title compound (Fig. 1).
In the Schiff base molecule, the acetohydrazide group (O1/N1/N2/C8/C9) is planar (r.m.s. deviation 0.034 Å) and it forms a dihedral angle of 8.81 (7)° with the benzene (C1-C6) ring. The molecule adopts a trans configuration with respect to the C═N bond. Bond lengths and angles are comparable to those observed for N'-[1-(4-methoxyphenyl)ethylidene]acetohydrazide (Li et al., 2008). An intramolecular O3—H3···O2 hydrogen bond is observed.
In the crystal, molecules are linked into a three-dimensional network (Fig.2) by O—H···O, N—H···O and C—H···O hydrogen bonds (Table 1).