Acta Cryst. (2009). E65, o678 [ doi:10.1107/S1600536809007272 ]
The title Schiff base compound, C13H8Cl3N3O2, was synthesized by the condensation reaction of 3,5-dichlorosalicylaldehyde with 6-chloronicotinic acid hydrazide in 95% ethanol. The molecule is nearly planar, with a dihedral angle of 1.9 (2)° between the aromatic ring planes, and an intramolecular O-H
N hydrogen bond is observed. In the crystal, the molecules are connected by intermolecular N-HO hydrogen bonds into infinite chains propagating in [100].
3,5-Dichlorosalicylaldehyde (0.1 mmol, 19.0 mg) and 6-chloronicotinic acid hydrazide (0.1 mmol, 17.1 mg) were dissolved in a 95% ethanol solution (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Light yellow blocks of (I) were formed by gradual evaporation of the solvent over a period of five days at room temperature.
All H atoms were placed in geometrically idealized positions, with C—H = 0.93 Å, O—H = 0.82 Å and N—H = 0.86 Å and refined as riding with Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(O).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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]](./hb2920fig1thm.gif)
| Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. The dashed lines indicate hydrogen bonds. |
![[Figure 2]](./hb2920fig2thm.gif)
| Fig. 2. The infinite chains structure formed via hydrogen bonds, H atoms have been omitted for clarity. The dashed lines indicate the connections between the donor and acceptor atoms of the hydrogen bonds. |
| C13H8Cl3N3O2 | F(000) = 696 |
| Mr = 344.57 | Dx = 1.627 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 669 reflections |
| a = 4.892 (1) Å | θ = 2.6–18.8° |
| b = 18.014 (4) Å | µ = 0.66 mm−1 |
| c = 16.112 (3) Å | T = 298 K |
| β = 97.90 (3)° | Block, light yellow |
| V = 1406.4 (5) Å3 | 0.27 × 0.23 × 0.23 mm |
| Z = 4 |
| Siemens SMART CCD diffractometer | 2478 independent reflections |
| Radiation source: fine-focus sealed tube | 1323 reflections with I > 2σ(I) |
| graphite | Rint = 0.078 |
| φ and ω scans | θmax = 25.1°, θmin = 1.7° |
| Absorption correction: multi-scan (SADABS; Siemens, 1996) | h = −5→5 |
| Tmin = 0.842, Tmax = 0.864 | k = −15→21 |
| 7275 measured reflections | l = −19→15 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.114 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0343P)2 + 0.2069P] where P = (Fo2 + 2Fc2)/3 |
| 2478 reflections | (Δ/σ)max = 0.001 |
| 191 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.40 e Å−3 |
| C13H8Cl3N3O2 | V = 1406.4 (5) Å3 |
| Mr = 344.57 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 4.892 (1) Å | µ = 0.66 mm−1 |
| b = 18.014 (4) Å | T = 298 K |
| c = 16.112 (3) Å | 0.27 × 0.23 × 0.23 mm |
| β = 97.90 (3)° |
| Siemens SMART CCD diffractometer | 2478 independent reflections |
| Absorption correction: multi-scan (SADABS; Siemens, 1996) | 1323 reflections with I > 2σ(I) |
| Tmin = 0.842, Tmax = 0.864 | Rint = 0.078 |
| 7275 measured reflections | θmax = 25.1° |
| R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.114 | Δρmax = 0.25 e Å−3 |
| S = 1.01 | Δρmin = −0.40 e Å−3 |
| 2478 reflections | Absolute structure: ? |
| 191 parameters | Flack parameter: ? |
| 0 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 | ||
| Cl1 | 0.3842 (2) | 0.62724 (6) | 0.45177 (7) | 0.0534 (3) | |
| Cl2 | 1.2166 (3) | 0.50424 (7) | 0.65897 (7) | 0.0651 (4) | |
| Cl3 | 1.2331 (3) | 1.28010 (7) | 0.69130 (8) | 0.0698 (4) | |
| N1 | 0.9665 (7) | 0.8466 (2) | 0.6071 (2) | 0.0471 (9) | |
| N2 | 1.0608 (7) | 0.91708 (18) | 0.6266 (2) | 0.0474 (9) | |
| H2 | 1.2318 | 0.9261 | 0.6437 | 0.057* | |
| O1 | 0.6119 (6) | 0.76626 (15) | 0.51866 (18) | 0.0542 (8) | |
| H1 | 0.6800 | 0.8046 | 0.5397 | 0.081* | |
| O2 | 0.6214 (6) | 0.95721 (16) | 0.59872 (19) | 0.0619 (9) | |
| C1 | 1.0059 (8) | 0.7165 (2) | 0.6081 (2) | 0.0408 (10) | |
| C2 | 0.7633 (8) | 0.7076 (2) | 0.5502 (2) | 0.0399 (10) | |
| C3 | 0.6750 (8) | 0.6374 (2) | 0.5262 (2) | 0.0411 (11) | |
| C4 | 0.8115 (8) | 0.5751 (2) | 0.5595 (3) | 0.0455 (11) | |
| H4 | 0.7479 | 0.5280 | 0.5428 | 0.055* | |
| C5 | 1.0456 (9) | 0.5834 (2) | 0.6182 (3) | 0.0461 (11) | |
| C6 | 1.1444 (9) | 0.6532 (2) | 0.6417 (3) | 0.0450 (11) | |
| H6 | 1.3036 | 0.6581 | 0.6801 | 0.054* | |
| C7 | 1.1106 (9) | 0.7906 (3) | 0.6314 (2) | 0.0452 (11) | |
| H7 | 1.2817 | 0.7964 | 0.6639 | 0.054* | |
| C8 | 0.8673 (9) | 0.9716 (2) | 0.6171 (3) | 0.0450 (11) | |
| C9 | 0.9672 (8) | 1.0483 (2) | 0.6324 (3) | 0.0410 (10) | |
| C10 | 0.8110 (9) | 1.1062 (2) | 0.5936 (3) | 0.0506 (12) | |
| H10 | 0.6519 | 1.0962 | 0.5566 | 0.061* | |
| C11 | 0.8935 (9) | 1.1786 (3) | 0.6102 (3) | 0.0543 (12) | |
| H11 | 0.7949 | 1.2183 | 0.5842 | 0.065* | |
| C12 | 1.1270 (9) | 1.1895 (2) | 0.6666 (3) | 0.0477 (12) | |
| N3 | 1.2807 (7) | 1.1365 (2) | 0.7059 (2) | 0.0502 (10) | |
| C13 | 1.1988 (9) | 1.0670 (2) | 0.6874 (3) | 0.0493 (11) | |
| H13 | 1.3051 | 1.0285 | 0.7133 | 0.059* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0452 (7) | 0.0496 (7) | 0.0632 (8) | −0.0075 (6) | 0.0002 (5) | −0.0027 (6) |
| Cl2 | 0.0715 (9) | 0.0529 (8) | 0.0676 (8) | 0.0141 (7) | −0.0015 (6) | 0.0027 (6) |
| Cl3 | 0.0842 (10) | 0.0520 (8) | 0.0722 (9) | −0.0184 (7) | 0.0071 (7) | −0.0060 (7) |
| N1 | 0.040 (2) | 0.040 (2) | 0.062 (3) | −0.0058 (19) | 0.0091 (18) | −0.0038 (19) |
| N2 | 0.036 (2) | 0.037 (2) | 0.067 (3) | −0.0058 (19) | −0.0010 (18) | −0.0074 (19) |
| O1 | 0.0454 (19) | 0.045 (2) | 0.069 (2) | −0.0041 (16) | −0.0032 (15) | −0.0010 (16) |
| O2 | 0.0317 (19) | 0.060 (2) | 0.092 (2) | −0.0082 (16) | 0.0027 (16) | −0.0115 (18) |
| C1 | 0.030 (2) | 0.045 (3) | 0.048 (3) | −0.004 (2) | 0.010 (2) | −0.005 (2) |
| C2 | 0.034 (3) | 0.035 (3) | 0.050 (3) | −0.002 (2) | 0.005 (2) | −0.001 (2) |
| C3 | 0.030 (2) | 0.049 (3) | 0.043 (3) | −0.002 (2) | 0.0032 (19) | 0.000 (2) |
| C4 | 0.048 (3) | 0.038 (3) | 0.053 (3) | −0.005 (2) | 0.016 (2) | −0.003 (2) |
| C5 | 0.048 (3) | 0.047 (3) | 0.044 (3) | 0.006 (2) | 0.010 (2) | 0.002 (2) |
| C6 | 0.041 (3) | 0.049 (3) | 0.045 (3) | 0.005 (2) | 0.007 (2) | −0.004 (2) |
| C7 | 0.035 (3) | 0.053 (3) | 0.048 (3) | −0.007 (2) | 0.006 (2) | −0.008 (2) |
| C8 | 0.040 (3) | 0.046 (3) | 0.049 (3) | −0.008 (2) | 0.006 (2) | −0.005 (2) |
| C9 | 0.033 (3) | 0.041 (3) | 0.049 (3) | −0.005 (2) | 0.006 (2) | −0.005 (2) |
| C10 | 0.041 (3) | 0.053 (3) | 0.055 (3) | −0.008 (2) | −0.001 (2) | −0.001 (2) |
| C11 | 0.053 (3) | 0.048 (3) | 0.061 (3) | −0.003 (2) | 0.003 (2) | 0.006 (2) |
| C12 | 0.052 (3) | 0.046 (3) | 0.047 (3) | −0.015 (2) | 0.013 (2) | −0.001 (2) |
| N3 | 0.043 (2) | 0.048 (3) | 0.057 (2) | −0.004 (2) | −0.0001 (18) | −0.006 (2) |
| C13 | 0.043 (3) | 0.044 (3) | 0.061 (3) | −0.002 (2) | 0.004 (2) | −0.006 (2) |
| Cl1—C3 | 1.739 (4) | C4—C5 | 1.389 (5) |
| Cl2—C5 | 1.736 (4) | C4—H4 | 0.9300 |
| Cl3—C12 | 1.742 (4) | C5—C6 | 1.382 (5) |
| N1—C7 | 1.263 (5) | C6—H6 | 0.9300 |
| N1—N2 | 1.372 (4) | C7—H7 | 0.9300 |
| N2—C8 | 1.358 (5) | C8—C9 | 1.474 (5) |
| N2—H2 | 0.8600 | C9—C13 | 1.380 (5) |
| O1—C2 | 1.349 (4) | C9—C10 | 1.391 (5) |
| O1—H1 | 0.8200 | C10—C11 | 1.380 (6) |
| O2—C8 | 1.227 (5) | C10—H10 | 0.9300 |
| C1—C6 | 1.396 (5) | C11—C12 | 1.373 (6) |
| C1—C2 | 1.414 (5) | C11—H11 | 0.9300 |
| C1—C7 | 1.460 (5) | C12—N3 | 1.321 (5) |
| C2—C3 | 1.375 (5) | N3—C13 | 1.337 (5) |
| C3—C4 | 1.376 (5) | C13—H13 | 0.9300 |
| C7—N1—N2 | 120.9 (4) | N1—C7—C1 | 119.3 (4) |
| C8—N2—N1 | 115.9 (4) | N1—C7—H7 | 120.3 |
| C8—N2—H2 | 122.1 | C1—C7—H7 | 120.3 |
| N1—N2—H2 | 122.1 | O2—C8—N2 | 121.3 (4) |
| C2—O1—H1 | 109.5 | O2—C8—C9 | 122.0 (4) |
| C6—C1—C2 | 118.8 (4) | N2—C8—C9 | 116.7 (4) |
| C6—C1—C7 | 120.8 (4) | C13—C9—C10 | 117.2 (4) |
| C2—C1—C7 | 120.4 (4) | C13—C9—C8 | 124.0 (4) |
| O1—C2—C3 | 118.6 (4) | C10—C9—C8 | 118.6 (4) |
| O1—C2—C1 | 121.8 (4) | C11—C10—C9 | 119.6 (4) |
| C3—C2—C1 | 119.5 (4) | C11—C10—H10 | 120.2 |
| C2—C3—C4 | 121.5 (4) | C9—C10—H10 | 120.2 |
| C2—C3—Cl1 | 119.1 (3) | C12—C11—C10 | 117.3 (4) |
| C4—C3—Cl1 | 119.4 (3) | C12—C11—H11 | 121.4 |
| C3—C4—C5 | 119.3 (4) | C10—C11—H11 | 121.4 |
| C3—C4—H4 | 120.4 | N3—C12—C11 | 125.5 (4) |
| C5—C4—H4 | 120.4 | N3—C12—Cl3 | 115.8 (3) |
| C6—C5—C4 | 120.6 (4) | C11—C12—Cl3 | 118.7 (4) |
| C6—C5—Cl2 | 120.8 (4) | C12—N3—C13 | 115.9 (4) |
| C4—C5—Cl2 | 118.6 (3) | N3—C13—C9 | 124.5 (4) |
| C5—C6—C1 | 120.3 (4) | N3—C13—H13 | 117.7 |
| C5—C6—H6 | 119.9 | C9—C13—H13 | 117.7 |
| C1—C6—H6 | 119.9 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O2i | 0.86 | 2.20 | 2.930 (4) | 142 |
| O1—H1···N1 | 0.82 | 1.82 | 2.540 (4) | 147 |
| Symmetry codes: (i) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O2i | 0.86 | 2.20 | 2.930 (4) | 142 |
| O1—H1···N1 | 0.82 | 1.82 | 2.540 (4) | 147 |
| Symmetry codes: (i) x+1, y, z. |
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Schiff base compounds have been widely investigated over a century (Fan et al., 2007; Kim et al., 2005). Some of the complexes derived from Schiff bases have been found to have pharmacological and antitumor properties (Ren et al., 2002; Takeuchi,et al., 1998). In this paper, the crystal structure of the title compound, (I), a new Schiff base compound derived from the condensation reaction of 3,5-dichlorosalicylaldehyde with 6-chloronicotinic acid hydrazide is reported.
The molecule of (I) displays a trans configuration with respect to the C=N and C—N bonds (Fig. 1). All the bond lengths are within normal ranges (Allen et al., 1987), and are comparable to those in the related compound 6-chloro-N'-(2-hydroxy-1-naphthylmethylene)nicotinohydrazide (Zhi 2008). The Schiff base molecule is nearly planar, with a dihedral angle between the benzene ring and the pyridine ring of 1.9 (2)°. An intramolecular O—H···N hydrogen bond is observed. The molecules are connected via intermolecular N—H···O hydrogen bonds into infinite chains along the a axis (Table 1, Fig. 2).