Acta Cryst. (2009). E65, o1465 [ doi:10.1107/S1600536809020078 ]
The title compound, C14H12N2O3·CH4O, consists of a Schiff base molecule and a methanol molecule of crystallization. The Schiff base molecule is nearly planar, the dihedral angle between the planes of the two benzene rings being 7.2 (2)°. The molecule exists in the trans configuration with respect to the methylidene unit. In the crystal structure, the Schiff base and methanol molecules are linked through O-H
O, N-HO and O-HN hydrogen bonds, forming a three-dimensional network.
The compound was prepared by refluxing 4-hydroxybenzaldehyde (1.0 mol) with 4-hydroxybenzohydrazide (1.0 mol) in methanol (100 ml). Excess methanol was removed from the mixture by distillation. The colorless solid product was filtered and washed three times with methanol. Colorless block crystals of the title compound were obtained from a methanol solution by slow evaporation in air.
H2A was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1)Å. Other H atoms were placed in calculated positions (C—H = 0.93 - 0.96 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O and methyl). A rotating group model was used for the methyl group of the methanol.
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]](./wn2329fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for the non-hydrogen atoms. Hydrogen atoms are shown as spheres of arbitrary radius. The dashed line indicates a hydrogen bond. |
![[Figure 2]](./wn2329fig2thm.gif)
| Fig. 2. The packing diagram, viewed along the b axis. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been omitted. |
| C14H12N2O3·CH4O | F(000) = 608 |
| Mr = 288.30 | Dx = 1.358 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2955 reflections |
| a = 12.927 (1) Å | θ = 2.7–29.4° |
| b = 9.277 (1) Å | µ = 0.10 mm−1 |
| c = 11.946 (2) Å | T = 298 K |
| β = 100.147 (1)° | Block, colorless |
| V = 1410.2 (3) Å3 | 0.30 × 0.30 × 0.28 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 3064 independent reflections |
| Radiation source: fine-focus sealed tube | 2382 reflections with I > 2σ(I) |
| graphite | Rint = 0.023 |
| ω scans | θmax = 27.0°, θmin = 1.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→16 |
| Tmin = 0.971, Tmax = 0.973 | k = −11→11 |
| 8435 measured reflections | l = −15→14 |
| 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) = 0.118 | w = 1/[σ2(Fo2) + (0.0556P)2 + 0.2974P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 3064 reflections | Δρmax = 0.22 e Å−3 |
| 197 parameters | Δρmin = −0.17 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: 0.0112 (19) |
| C14H12N2O3·CH4O | V = 1410.2 (3) Å3 |
| Mr = 288.30 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.927 (1) Å | µ = 0.10 mm−1 |
| b = 9.277 (1) Å | T = 298 K |
| c = 11.946 (2) Å | 0.30 × 0.30 × 0.28 mm |
| β = 100.147 (1)° |
| Bruker SMART CCD area-detector diffractometer | 3064 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2382 reflections with I > 2σ(I) |
| Tmin = 0.971, Tmax = 0.973 | Rint = 0.023 |
| 8435 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.118 | Δρmax = 0.22 e Å−3 |
| S = 1.06 | Δρmin = −0.17 e Å−3 |
| 3064 reflections | Absolute structure: ? |
| 197 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 | 0.70137 (9) | 0.02841 (13) | 0.10898 (10) | 0.0378 (3) | |
| N2 | 0.78657 (9) | 0.08908 (13) | 0.07052 (10) | 0.0383 (3) | |
| O1 | 0.30453 (8) | −0.37263 (12) | 0.13979 (9) | 0.0485 (3) | |
| H1 | 0.2840 | −0.3402 | 0.1959 | 0.073* | |
| O2 | 0.80648 (8) | 0.24758 (12) | 0.21426 (9) | 0.0475 (3) | |
| O3 | 1.21247 (9) | 0.40526 (14) | 0.01129 (11) | 0.0588 (4) | |
| H3 | 1.2348 | 0.4747 | 0.0508 | 0.088* | |
| O4 | 0.79337 (10) | 0.50038 (13) | 0.33324 (9) | 0.0565 (3) | |
| H4 | 0.8007 | 0.4286 | 0.2953 | 0.085* | |
| C1 | 0.56666 (10) | −0.15101 (15) | 0.07692 (11) | 0.0352 (3) | |
| C2 | 0.52247 (11) | −0.11701 (16) | 0.17196 (12) | 0.0413 (4) | |
| H2 | 0.5519 | −0.0441 | 0.2208 | 0.050* | |
| C3 | 0.43564 (11) | −0.19027 (17) | 0.19437 (12) | 0.0410 (3) | |
| H3A | 0.4071 | −0.1669 | 0.2582 | 0.049* | |
| C4 | 0.39100 (10) | −0.29833 (15) | 0.12210 (11) | 0.0342 (3) | |
| C5 | 0.43415 (12) | −0.33417 (17) | 0.02789 (13) | 0.0429 (4) | |
| H5 | 0.4046 | −0.4072 | −0.0208 | 0.052* | |
| C6 | 0.52155 (11) | −0.26075 (17) | 0.00652 (12) | 0.0432 (4) | |
| H6 | 0.5507 | −0.2857 | −0.0566 | 0.052* | |
| C7 | 0.65706 (11) | −0.07482 (16) | 0.04877 (12) | 0.0392 (3) | |
| H7 | 0.6834 | −0.1026 | −0.0156 | 0.047* | |
| C8 | 0.83705 (10) | 0.19889 (15) | 0.12912 (12) | 0.0347 (3) | |
| C9 | 0.93302 (10) | 0.25557 (14) | 0.09212 (11) | 0.0341 (3) | |
| C10 | 0.98624 (11) | 0.36828 (16) | 0.15352 (13) | 0.0420 (4) | |
| H10 | 0.9590 | 0.4089 | 0.2133 | 0.050* | |
| C11 | 1.07881 (12) | 0.42096 (17) | 0.12748 (13) | 0.0443 (4) | |
| H11 | 1.1135 | 0.4966 | 0.1694 | 0.053* | |
| C12 | 1.11995 (11) | 0.36095 (16) | 0.03881 (13) | 0.0403 (3) | |
| C13 | 1.06694 (12) | 0.25061 (17) | −0.02465 (13) | 0.0451 (4) | |
| H13 | 1.0938 | 0.2116 | −0.0853 | 0.054* | |
| C14 | 0.97452 (11) | 0.19819 (16) | 0.00163 (12) | 0.0413 (4) | |
| H14 | 0.9394 | 0.1238 | −0.0414 | 0.050* | |
| C15 | 0.74278 (19) | 0.6095 (2) | 0.26152 (16) | 0.0737 (6) | |
| H15A | 0.7498 | 0.6999 | 0.3012 | 0.111* | |
| H15B | 0.6696 | 0.5862 | 0.2397 | 0.111* | |
| H15C | 0.7745 | 0.6166 | 0.1948 | 0.111* | |
| H2A | 0.8014 (16) | 0.059 (2) | 0.0042 (11) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0316 (6) | 0.0421 (7) | 0.0427 (6) | −0.0080 (5) | 0.0150 (5) | 0.0011 (5) |
| N2 | 0.0346 (6) | 0.0438 (7) | 0.0406 (7) | −0.0115 (5) | 0.0174 (5) | −0.0034 (5) |
| O1 | 0.0437 (6) | 0.0549 (7) | 0.0533 (7) | −0.0208 (5) | 0.0262 (5) | −0.0121 (5) |
| O2 | 0.0476 (6) | 0.0488 (6) | 0.0528 (6) | −0.0110 (5) | 0.0271 (5) | −0.0127 (5) |
| O3 | 0.0459 (6) | 0.0687 (8) | 0.0696 (8) | −0.0257 (6) | 0.0318 (6) | −0.0206 (6) |
| O4 | 0.0673 (8) | 0.0592 (7) | 0.0440 (6) | 0.0072 (6) | 0.0124 (5) | −0.0073 (5) |
| C1 | 0.0315 (7) | 0.0377 (7) | 0.0382 (7) | −0.0047 (6) | 0.0111 (6) | 0.0015 (6) |
| C2 | 0.0394 (8) | 0.0447 (8) | 0.0421 (8) | −0.0109 (6) | 0.0135 (6) | −0.0096 (6) |
| C3 | 0.0390 (8) | 0.0501 (9) | 0.0379 (7) | −0.0068 (6) | 0.0178 (6) | −0.0062 (6) |
| C4 | 0.0297 (7) | 0.0365 (7) | 0.0387 (7) | −0.0042 (5) | 0.0123 (6) | 0.0025 (6) |
| C5 | 0.0427 (8) | 0.0450 (8) | 0.0445 (8) | −0.0149 (7) | 0.0170 (6) | −0.0126 (7) |
| C6 | 0.0441 (8) | 0.0498 (9) | 0.0405 (8) | −0.0097 (7) | 0.0213 (7) | −0.0085 (7) |
| C7 | 0.0364 (7) | 0.0452 (8) | 0.0392 (7) | −0.0076 (6) | 0.0154 (6) | −0.0015 (6) |
| C8 | 0.0319 (7) | 0.0348 (7) | 0.0395 (7) | −0.0012 (6) | 0.0122 (6) | 0.0009 (6) |
| C9 | 0.0306 (7) | 0.0351 (7) | 0.0382 (7) | −0.0029 (5) | 0.0106 (6) | 0.0015 (6) |
| C10 | 0.0396 (8) | 0.0460 (8) | 0.0440 (8) | −0.0073 (6) | 0.0174 (6) | −0.0085 (6) |
| C11 | 0.0404 (8) | 0.0463 (8) | 0.0487 (9) | −0.0146 (7) | 0.0144 (7) | −0.0118 (7) |
| C12 | 0.0339 (7) | 0.0438 (8) | 0.0462 (8) | −0.0084 (6) | 0.0148 (6) | 0.0001 (6) |
| C13 | 0.0423 (8) | 0.0507 (9) | 0.0475 (8) | −0.0093 (7) | 0.0217 (7) | −0.0115 (7) |
| C14 | 0.0390 (8) | 0.0413 (8) | 0.0462 (8) | −0.0117 (6) | 0.0146 (6) | −0.0097 (6) |
| C15 | 0.1079 (17) | 0.0625 (12) | 0.0508 (11) | −0.0016 (11) | 0.0144 (11) | 0.0044 (9) |
| N1—C7 | 1.2718 (18) | C5—C6 | 1.3810 (19) |
| N1—N2 | 1.3853 (15) | C5—H5 | 0.9300 |
| N2—C8 | 1.3390 (18) | C6—H6 | 0.9300 |
| N2—H2A | 0.892 (9) | C7—H7 | 0.9300 |
| O1—C4 | 1.3611 (16) | C8—C9 | 1.4846 (18) |
| O1—H1 | 0.8200 | C9—C10 | 1.3881 (19) |
| O2—C8 | 1.2395 (16) | C9—C14 | 1.3943 (19) |
| O3—C12 | 1.3587 (16) | C10—C11 | 1.3780 (19) |
| O3—H3 | 0.8200 | C10—H10 | 0.9300 |
| O4—C15 | 1.410 (2) | C11—C12 | 1.383 (2) |
| O4—H4 | 0.8200 | C11—H11 | 0.9300 |
| C1—C6 | 1.382 (2) | C12—C13 | 1.382 (2) |
| C1—C2 | 1.3939 (19) | C13—C14 | 1.376 (2) |
| C1—C7 | 1.4549 (18) | C13—H13 | 0.9300 |
| C2—C3 | 1.3782 (19) | C14—H14 | 0.9300 |
| C2—H2 | 0.9300 | C15—H15A | 0.9600 |
| C3—C4 | 1.381 (2) | C15—H15B | 0.9600 |
| C3—H3A | 0.9300 | C15—H15C | 0.9600 |
| C4—C5 | 1.3817 (19) | ||
| C7—N1—N2 | 115.06 (11) | O2—C8—N2 | 120.65 (12) |
| C8—N2—N1 | 118.58 (11) | O2—C8—C9 | 121.28 (13) |
| C8—N2—H2A | 122.8 (14) | N2—C8—C9 | 118.01 (11) |
| N1—N2—H2A | 118.4 (14) | C10—C9—C14 | 118.34 (12) |
| C4—O1—H1 | 109.5 | C10—C9—C8 | 118.16 (12) |
| C12—O3—H3 | 109.5 | C14—C9—C8 | 123.46 (12) |
| C15—O4—H4 | 109.5 | C11—C10—C9 | 121.15 (13) |
| C6—C1—C2 | 118.21 (12) | C11—C10—H10 | 119.4 |
| C6—C1—C7 | 119.15 (12) | C9—C10—H10 | 119.4 |
| C2—C1—C7 | 122.64 (13) | C10—C11—C12 | 119.76 (14) |
| C3—C2—C1 | 120.74 (13) | C10—C11—H11 | 120.1 |
| C3—C2—H2 | 119.6 | C12—C11—H11 | 120.1 |
| C1—C2—H2 | 119.6 | O3—C12—C13 | 117.65 (13) |
| C2—C3—C4 | 120.09 (12) | O3—C12—C11 | 122.48 (13) |
| C2—C3—H3A | 120.0 | C13—C12—C11 | 119.87 (13) |
| C4—C3—H3A | 120.0 | C14—C13—C12 | 120.20 (13) |
| O1—C4—C3 | 122.32 (12) | C14—C13—H13 | 119.9 |
| O1—C4—C5 | 117.71 (13) | C12—C13—H13 | 119.9 |
| C3—C4—C5 | 119.97 (12) | C13—C14—C9 | 120.66 (13) |
| C6—C5—C4 | 119.52 (13) | C13—C14—H14 | 119.7 |
| C6—C5—H5 | 120.2 | C9—C14—H14 | 119.7 |
| C4—C5—H5 | 120.2 | O4—C15—H15A | 109.5 |
| C5—C6—C1 | 121.46 (13) | O4—C15—H15B | 109.5 |
| C5—C6—H6 | 119.3 | H15A—C15—H15B | 109.5 |
| C1—C6—H6 | 119.3 | O4—C15—H15C | 109.5 |
| N1—C7—C1 | 122.36 (13) | H15A—C15—H15C | 109.5 |
| N1—C7—H7 | 118.8 | H15B—C15—H15C | 109.5 |
| C1—C7—H7 | 118.8 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.82 | 1.90 | 2.6877 (14) | 160 |
| O1—H1···N1i | 0.82 | 2.61 | 3.1521 (16) | 125 |
| O3—H3···O1ii | 0.82 | 1.90 | 2.7156 (15) | 172 |
| O4—H4···O2 | 0.82 | 1.95 | 2.7629 (15) | 173 |
| N2—H2A···O4iii | 0.89 (1) | 2.10 (1) | 2.9695 (16) | 165 (2) |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y+1, z; (iii) x, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.82 | 1.90 | 2.6877 (14) | 160 |
| O1—H1···N1i | 0.82 | 2.61 | 3.1521 (16) | 125 |
| O3—H3···O1ii | 0.82 | 1.90 | 2.7156 (15) | 172 |
| O4—H4···O2 | 0.82 | 1.95 | 2.7629 (15) | 173 |
| N2—H2A···O4iii | 0.89 (1) | 2.10 (1) | 2.9695 (16) | 165 (2) |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y+1, z; (iii) x, −y+1/2, z−1/2. |
Financial support of this work was provided 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 shown 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, many Schiff bases have been synthesized and structurally characterized (Yehye et al., 2008; Fun, Patil, Jebas et al. (2008); Fun, Patil, Rao et al. (2008); Yang et al., 2008; Ejsmont et al., 2008). Recently, we have reported a few such compounds (Ban & Li, 2008a,b; Li & Ban, 2009a,b). In this paper, we report the crystal structure of the new title compound.
In the structure of the title compound (Fig. 1) the Schiff base molecule is nearly planar, the dihedral angle between the two benzene rings being 7.2 (2)°. The molecule exists in a trans configuration with respect to the methylidene unit. The torsion angle C7—N1—N2—C8 is 0.3 (2)°.
In the crystal structure, the Schiff base molecules and the methanol molecules are linked through intermolecular O—H···O, N—H···O and O—H···N hydrogen bonds (Table 1), forming a three dimensional network (Fig. 2).