Acta Cryst. (2009). E65, o975 [ doi:10.1107/S160053680901215X ]
The title Schiff base compound, C14H11ClN2O3, was prepared by the reaction of 5-chlorosalicylaldehyde and 4-hydroxybenzohydrazide. The molecule exists in a trans configuration with respect to the methylidene group. The dihedral angle between the two benzene rings is 40.1 (2)°. An intramolecular O-H
N hydrogen bond helps to stabilize the molecular conformation. In the crystal structure, molecules are linked into a three-dimensional network by intermolecular N-HO and O-HO hydrogen bonds.
The title compound was prepared by the Schiff base condensation of equimolar amounts (0.5 mmol each) of 5-chlorosalicylaldehyde and 4-hydroxybenzohydrazide in methanol (20 ml). Excess methanol was removed from the reaction mixture by distillation. The colourless solid was filtered and dried in air. Colourless block-shaped crystals suitable for X-ray diffraction were obtained from a methanol solution.
The imino H atoms were located in a difference map and refined with N–H distances restrained to 0.90 (1) Å. The remaining H atoms were positioned geometrically [C–H = 0.93 Å, O–H = 0.82 Å] and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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]](./sj2605fig1thm.gif)
| Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./sj2605fig2thm.gif)
| Fig. 2. The crystal packing of (I), viewed along the b axis with hydrogen bonds drawn as dashed lines. |
| C14H11ClN2O3 | F(000) = 600 |
| Mr = 290.70 | Dx = 1.513 Mg m−3 |
| Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2c -2n | Cell parameters from 4763 reflections |
| a = 9.423 (1) Å | θ = 2.5–30.6° |
| b = 9.839 (1) Å | µ = 0.31 mm−1 |
| c = 13.770 (1) Å | T = 298 K |
| V = 1276.7 (2) Å3 | Block, colourless |
| Z = 4 | 0.17 × 0.15 × 0.15 mm |
| Bruker SMART CCD diffractometer | 2231 independent reflections |
| Radiation source: fine-focus sealed tube | 2144 reflections with I > 2σ(I) |
| graphite | Rint = 0.022 |
| ω scans | θmax = 27.0°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→11 |
| Tmin = 0.950, Tmax = 0.955 | k = −12→12 |
| 7398 measured reflections | l = −17→11 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0409P)2 + 0.1827P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.071 | (Δ/σ)max = 0.001 |
| S = 1.06 | Δρmax = 0.21 e Å−3 |
| 2231 reflections | Δρmin = −0.32 e Å−3 |
| 187 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 2 restraints | Extinction coefficient: 0.034 (3) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 784 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: −0.01 (6) |
| C14H11ClN2O3 | V = 1276.7 (2) Å3 |
| Mr = 290.70 | Z = 4 |
| Orthorhombic, Pna21 | Mo Kα radiation |
| a = 9.423 (1) Å | µ = 0.31 mm−1 |
| b = 9.839 (1) Å | T = 298 K |
| c = 13.770 (1) Å | 0.17 × 0.15 × 0.15 mm |
| Bruker SMART CCD diffractometer | 2231 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2144 reflections with I > 2σ(I) |
| Tmin = 0.950, Tmax = 0.955 | Rint = 0.022 |
| 7398 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.071 | Δρmax = 0.21 e Å−3 |
| S = 1.06 | Δρmin = −0.32 e Å−3 |
| 2231 reflections | Absolute structure: Flack (1983), 784 Friedel pairs |
| 187 parameters | Flack parameter: −0.01 (6) |
| 2 restraints |
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 | ||
| Cl1 | 0.74914 (6) | 0.47741 (5) | 1.21657 (5) | 0.05224 (15) | |
| N1 | 0.99352 (15) | 0.30628 (14) | 0.80967 (10) | 0.0316 (3) | |
| N2 | 0.94949 (14) | 0.28112 (13) | 0.71621 (12) | 0.0319 (3) | |
| O1 | 1.19292 (14) | 0.32175 (17) | 0.94031 (11) | 0.0504 (4) | |
| H1 | 1.1598 | 0.3057 | 0.8865 | 0.076* | |
| O2 | 1.14143 (12) | 0.14658 (12) | 0.69247 (10) | 0.0370 (3) | |
| O3 | 0.84616 (17) | 0.10538 (15) | 0.27816 (10) | 0.0505 (4) | |
| H3 | 0.8733 | 0.0312 | 0.2583 | 0.076* | |
| C1 | 0.94953 (17) | 0.38640 (15) | 0.96863 (13) | 0.0312 (3) | |
| C2 | 1.08639 (18) | 0.35624 (17) | 1.00215 (14) | 0.0346 (4) | |
| C3 | 1.1165 (2) | 0.36019 (19) | 1.10078 (15) | 0.0403 (4) | |
| H3A | 1.2072 | 0.3386 | 1.1225 | 0.048* | |
| C4 | 1.0133 (2) | 0.39569 (17) | 1.16663 (14) | 0.0391 (4) | |
| H4 | 1.0332 | 0.3960 | 1.2328 | 0.047* | |
| C5 | 0.87956 (19) | 0.43088 (17) | 1.13363 (14) | 0.0362 (4) | |
| C6 | 0.84744 (18) | 0.42738 (18) | 1.03619 (14) | 0.0352 (4) | |
| H6 | 0.7573 | 0.4524 | 1.0152 | 0.042* | |
| C7 | 0.90835 (18) | 0.36642 (16) | 0.86788 (13) | 0.0325 (3) | |
| H7 | 0.8207 | 0.3972 | 0.8459 | 0.039* | |
| C8 | 1.03211 (17) | 0.20101 (16) | 0.65983 (13) | 0.0292 (3) | |
| C9 | 0.98366 (16) | 0.17900 (16) | 0.55911 (12) | 0.0296 (3) | |
| C10 | 1.03520 (17) | 0.06631 (17) | 0.50845 (14) | 0.0335 (4) | |
| H10 | 1.0998 | 0.0084 | 0.5384 | 0.040* | |
| C11 | 0.99177 (18) | 0.03955 (17) | 0.41486 (14) | 0.0350 (4) | |
| H11 | 1.0265 | −0.0361 | 0.3821 | 0.042* | |
| C12 | 0.89604 (19) | 0.12597 (18) | 0.36973 (13) | 0.0352 (4) | |
| C13 | 0.8457 (2) | 0.2394 (2) | 0.41833 (15) | 0.0450 (5) | |
| H13 | 0.7826 | 0.2980 | 0.3876 | 0.054* | |
| C14 | 0.8889 (2) | 0.26545 (18) | 0.51195 (14) | 0.0392 (4) | |
| H14 | 0.8544 | 0.3417 | 0.5441 | 0.047* | |
| H2 | 0.8598 (14) | 0.303 (3) | 0.703 (2) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0578 (3) | 0.0676 (3) | 0.0313 (2) | 0.0148 (2) | 0.0054 (2) | −0.0062 (3) |
| N1 | 0.0343 (7) | 0.0371 (7) | 0.0235 (8) | −0.0016 (5) | −0.0046 (6) | −0.0003 (6) |
| N2 | 0.0319 (7) | 0.0408 (7) | 0.0229 (7) | 0.0001 (5) | −0.0045 (7) | −0.0009 (6) |
| O1 | 0.0365 (7) | 0.0791 (10) | 0.0354 (8) | 0.0131 (7) | −0.0033 (6) | −0.0060 (7) |
| O2 | 0.0323 (6) | 0.0466 (6) | 0.0322 (7) | 0.0039 (5) | −0.0061 (5) | 0.0025 (5) |
| O3 | 0.0679 (10) | 0.0545 (8) | 0.0289 (8) | 0.0089 (6) | −0.0118 (7) | −0.0097 (6) |
| C1 | 0.0344 (8) | 0.0322 (8) | 0.0271 (9) | −0.0001 (6) | −0.0049 (7) | −0.0006 (6) |
| C2 | 0.0352 (8) | 0.0376 (8) | 0.0311 (9) | 0.0014 (6) | −0.0033 (8) | −0.0024 (7) |
| C3 | 0.0400 (10) | 0.0450 (9) | 0.0358 (11) | 0.0036 (7) | −0.0127 (8) | −0.0025 (8) |
| C4 | 0.0531 (11) | 0.0398 (8) | 0.0244 (9) | 0.0025 (7) | −0.0103 (8) | −0.0032 (7) |
| C5 | 0.0444 (9) | 0.0359 (8) | 0.0283 (9) | 0.0031 (7) | 0.0005 (7) | −0.0044 (7) |
| C6 | 0.0350 (8) | 0.0406 (8) | 0.0300 (9) | 0.0035 (7) | −0.0046 (7) | −0.0008 (7) |
| C7 | 0.0317 (8) | 0.0386 (8) | 0.0271 (9) | 0.0007 (6) | −0.0056 (7) | 0.0011 (7) |
| C8 | 0.0298 (8) | 0.0318 (7) | 0.0261 (9) | −0.0043 (6) | −0.0007 (6) | 0.0027 (6) |
| C9 | 0.0304 (7) | 0.0342 (7) | 0.0243 (9) | −0.0013 (6) | 0.0003 (6) | 0.0019 (6) |
| C10 | 0.0309 (8) | 0.0371 (8) | 0.0327 (10) | 0.0039 (6) | −0.0011 (7) | −0.0011 (7) |
| C11 | 0.0358 (9) | 0.0370 (8) | 0.0321 (10) | 0.0015 (6) | 0.0030 (7) | −0.0058 (7) |
| C12 | 0.0392 (9) | 0.0426 (9) | 0.0239 (9) | −0.0033 (7) | −0.0011 (7) | −0.0004 (7) |
| C13 | 0.0593 (12) | 0.0446 (9) | 0.0311 (10) | 0.0158 (8) | −0.0110 (9) | 0.0004 (8) |
| C14 | 0.0527 (10) | 0.0360 (8) | 0.0290 (9) | 0.0111 (7) | −0.0052 (8) | −0.0040 (7) |
| Cl1—C5 | 1.7391 (19) | C4—C5 | 1.384 (3) |
| N1—C7 | 1.279 (2) | C4—H4 | 0.9300 |
| N1—N2 | 1.375 (2) | C5—C6 | 1.376 (3) |
| N2—C8 | 1.353 (2) | C6—H6 | 0.9300 |
| N2—H2 | 0.892 (10) | C7—H7 | 0.9300 |
| O1—C2 | 1.359 (2) | C8—C9 | 1.476 (2) |
| O1—H1 | 0.8200 | C9—C14 | 1.394 (2) |
| O2—C8 | 1.245 (2) | C9—C10 | 1.397 (2) |
| O3—C12 | 1.361 (2) | C10—C11 | 1.378 (3) |
| O3—H3 | 0.8200 | C10—H10 | 0.9300 |
| C1—C6 | 1.398 (2) | C11—C12 | 1.387 (2) |
| C1—C2 | 1.402 (2) | C11—H11 | 0.9300 |
| C1—C7 | 1.454 (2) | C12—C13 | 1.385 (3) |
| C2—C3 | 1.388 (3) | C13—C14 | 1.376 (3) |
| C3—C4 | 1.374 (3) | C13—H13 | 0.9300 |
| C3—H3A | 0.9300 | C14—H14 | 0.9300 |
| C7—N1—N2 | 118.72 (14) | N1—C7—C1 | 119.54 (15) |
| C8—N2—N1 | 117.94 (13) | N1—C7—H7 | 120.2 |
| C8—N2—H2 | 125 (2) | C1—C7—H7 | 120.2 |
| N1—N2—H2 | 116 (2) | O2—C8—N2 | 121.31 (16) |
| C2—O1—H1 | 109.5 | O2—C8—C9 | 122.14 (15) |
| C12—O3—H3 | 109.5 | N2—C8—C9 | 116.53 (14) |
| C6—C1—C2 | 118.37 (16) | C14—C9—C10 | 118.32 (16) |
| C6—C1—C7 | 119.37 (15) | C14—C9—C8 | 123.12 (15) |
| C2—C1—C7 | 122.09 (16) | C10—C9—C8 | 118.56 (14) |
| O1—C2—C3 | 117.99 (16) | C11—C10—C9 | 121.03 (16) |
| O1—C2—C1 | 121.73 (17) | C11—C10—H10 | 119.5 |
| C3—C2—C1 | 120.28 (16) | C9—C10—H10 | 119.5 |
| C4—C3—C2 | 120.55 (16) | C10—C11—C12 | 119.69 (16) |
| C4—C3—H3A | 119.7 | C10—C11—H11 | 120.2 |
| C2—C3—H3A | 119.7 | C12—C11—H11 | 120.2 |
| C3—C4—C5 | 119.41 (17) | O3—C12—C13 | 116.71 (16) |
| C3—C4—H4 | 120.3 | O3—C12—C11 | 123.28 (16) |
| C5—C4—H4 | 120.3 | C13—C12—C11 | 120.01 (17) |
| C6—C5—C4 | 120.95 (18) | C14—C13—C12 | 120.13 (17) |
| C6—C5—Cl1 | 119.44 (14) | C14—C13—H13 | 119.9 |
| C4—C5—Cl1 | 119.59 (15) | C12—C13—H13 | 119.9 |
| C5—C6—C1 | 120.32 (16) | C13—C14—C9 | 120.80 (16) |
| C5—C6—H6 | 119.8 | C13—C14—H14 | 119.6 |
| C1—C6—H6 | 119.8 | C9—C14—H14 | 119.6 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O2i | 0.89 (1) | 2.12 (1) | 3.0065 (18) | 172 (3) |
| O3—H3···O2ii | 0.82 | 1.98 | 2.7479 (19) | 157 |
| O1—H1···N1 | 0.82 | 1.89 | 2.6057 (19) | 145 |
| Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+2, −y, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O2i | 0.89 (1) | 2.12 (1) | 3.0065 (18) | 172 (3) |
| O3—H3···O2ii | 0.82 | 1.98 | 2.7479 (19) | 157 |
| O1—H1···N1 | 0.82 | 1.89 | 2.6057 (19) | 145 |
| Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+2, −y, z−1/2. |
The author acknowledges the Natural Science Foundation of the Education Office of Anhui Province (Project No. 2009 A150020).
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Hyrazone compounds, derived from the reaction of aldehydes with hydrazides, have been widely studied due to their excellent biological properties (Bedia et al., 2006; Rollas et al., 2002; Fun et al., 2008). Recently, we have reported several Schiff base hydrazone compounds (Qiu, Fang et al., 2006; Qiu, Luo et al., 2006a,b; Qiu, Xu et al., 2006), and we report herein the crystal structure of the new title compound, (I), Fig. 1.
The molecule in (I) exists in a trans configuration with respect to the methylidene group. The dihedral angle between the two benzene rings is 40.1 (2)°. The bond lengths in (I) are found to have normal values (Allen et al., 1987) and are comparable to the values found in similar compounds (Singh et al., 2007; Narayana et al., 2007; Cui et al., 2007; Diao et al., 2008).
An intramolecular O–H···N hydrogen bond (Table 1) helps to stabilize the molecular conformation. In the crystal structure, molecules are linked into a three-dimensional network by intermolecular N–H···O and O–H···O hydrogen bonds (Table 1 and Fig. 2).