Acta Cryst. (2012). E68, o2323 [ doi:10.1107/S1600536812029443 ]
The title compound, C17H14Cl4N2O2, is generated by crystallographic twofold symmetry. The two benzene rings are inclined to one another by 80.17 (10)°. There are two intramolecular O-H
N hydrogen bonds, which make S(6) ring motifs. In the crystal, molecules are linked by C-HO and weak C-HCl interactions, forming a three-dimensional network.
The title compound was synthesized by adding 3,5-dichlorosalicylaldehyde (2 mmol) to a solution of propylenediamine (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for 30 min. The resultant solution was filtered. Light-yellow prismatic single crystals of the title compound, suitable for X-ray structure determination, were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.
The OH and C-bound H atoms were included in calculated positions and treated as riding atoms: O-H = 0.82 Å, C-H = 0.93 and 0.96 Å, with Uiso(H) = k × Ueq(O,C) where k = 1.5 for OH and CH3 H atoms and = 1.2 for other H atoms.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2009).
![[Figure 1]](./su2464fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering [symmetry code for suffix A = -x, -y, z]. |
![[Figure 2]](./su2464fig2thm.gif)
| Fig. 2. The crystal packing diagram of the title compound viewed down the c-axis, showing linking of molecules through C—H···O and weak C—H···Cl interactions (dashed lines). |
| C17H14Cl4N2O2 | F(000) = 1712 |
| Mr = 420.10 | Dx = 1.586 Mg m−3 |
| Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: F 2 -2d | Cell parameters from 1234 reflections |
| a = 24.9797 (14) Å | θ = 2.5–27.5° |
| b = 31.666 (3) Å | µ = 0.69 mm−1 |
| c = 4.4495 (2) Å | T = 291 K |
| V = 3519.6 (4) Å3 | Prism, light-yellow |
| Z = 8 | 0.26 × 0.23 × 0.18 mm |
| Bruker SMART APEXII CCD area-detector diffractometer | 1960 independent reflections |
| Radiation source: fine-focus sealed tube | 1634 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| φ and ω scans | θmax = 27.3°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −32→32 |
| Tmin = 0.842, Tmax = 0.886 | k = −40→40 |
| 7926 measured reflections | l = −5→5 |
| 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)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0306P)2 + 1.6825P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 1960 reflections | Δρmax = 0.14 e Å−3 |
| 115 parameters | Δρmin = −0.16 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 842 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.08 (7) |
| C17H14Cl4N2O2 | V = 3519.6 (4) Å3 |
| Mr = 420.10 | Z = 8 |
| Orthorhombic, Fdd2 | Mo Kα radiation |
| a = 24.9797 (14) Å | µ = 0.69 mm−1 |
| b = 31.666 (3) Å | T = 291 K |
| c = 4.4495 (2) Å | 0.26 × 0.23 × 0.18 mm |
| Bruker SMART APEXII CCD area-detector diffractometer | 1960 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1634 reflections with I > 2σ(I) |
| Tmin = 0.842, Tmax = 0.886 | Rint = 0.028 |
| 7926 measured reflections | θmax = 27.3° |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.068 | Δρmax = 0.14 e Å−3 |
| S = 1.04 | Δρmin = −0.16 e Å−3 |
| 1960 reflections | Absolute structure: Flack (1983), 842 Friedel pairs |
| 115 parameters | Flack parameter: 0.08 (7) |
| 1 restraint |
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 | Occ. (<1) | |
| C1 | −0.04810 (7) | 0.14212 (6) | 0.7828 (4) | 0.0378 (4) | |
| C2 | −0.05597 (7) | 0.17577 (6) | 0.5854 (5) | 0.0405 (5) | |
| C3 | −0.01420 (7) | 0.19985 (6) | 0.4810 (5) | 0.0429 (5) | |
| H9 | −0.0203 | 0.2218 | 0.3466 | 0.052* | |
| C4 | 0.03720 (8) | 0.19078 (6) | 0.5799 (5) | 0.0419 (5) | |
| C5 | 0.04673 (7) | 0.15902 (6) | 0.7793 (5) | 0.0409 (5) | |
| H2 | 0.0814 | 0.1538 | 0.8453 | 0.049* | |
| C6 | 0.00437 (7) | 0.13440 (6) | 0.8845 (4) | 0.0374 (4) | |
| C7 | 0.01466 (8) | 0.10036 (6) | 1.0958 (4) | 0.0401 (5) | |
| H4 | 0.0489 | 0.0972 | 1.1753 | 0.048* | |
| C8 | −0.00878 (9) | 0.03959 (6) | 1.3730 (4) | 0.0458 (5) | |
| H5A | −0.0378 | 0.0351 | 1.5143 | 0.055* | |
| H5B | 0.0234 | 0.0461 | 1.4863 | 0.055* | |
| C9 | 0.0000 | 0.0000 | 1.1876 (7) | 0.0465 (7) | |
| H6A | −0.0309 | −0.0043 | 1.0589 | 0.056* | 0.50 |
| H6B | 0.0309 | 0.0043 | 1.0589 | 0.056* | 0.50 |
| Cl1 | −0.12035 (2) | 0.187207 (19) | 0.46609 (15) | 0.05937 (17) | |
| Cl2 | 0.09006 (2) | 0.220654 (18) | 0.43888 (16) | 0.06188 (18) | |
| N1 | −0.02186 (7) | 0.07479 (5) | 1.1743 (4) | 0.0424 (4) | |
| O1 | −0.08951 (5) | 0.11861 (4) | 0.8692 (4) | 0.0503 (4) | |
| H1 | −0.0790 | 0.0999 | 0.9826 | 0.075* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0349 (9) | 0.0355 (9) | 0.0429 (12) | −0.0002 (8) | −0.0034 (8) | −0.0052 (9) |
| C2 | 0.0322 (9) | 0.0401 (10) | 0.0490 (12) | 0.0056 (8) | −0.0083 (8) | −0.0044 (9) |
| C3 | 0.0415 (10) | 0.0356 (9) | 0.0518 (13) | 0.0015 (8) | −0.0029 (10) | 0.0001 (10) |
| C4 | 0.0349 (10) | 0.0359 (10) | 0.0550 (13) | −0.0016 (8) | 0.0015 (9) | −0.0067 (9) |
| C5 | 0.0314 (9) | 0.0402 (10) | 0.0512 (13) | 0.0052 (8) | −0.0060 (8) | −0.0087 (9) |
| C6 | 0.0368 (9) | 0.0344 (9) | 0.0409 (11) | 0.0028 (7) | −0.0035 (8) | −0.0085 (9) |
| C7 | 0.0374 (10) | 0.0420 (11) | 0.0410 (11) | 0.0067 (8) | −0.0083 (8) | −0.0084 (9) |
| C8 | 0.0521 (12) | 0.0446 (11) | 0.0407 (12) | 0.0032 (9) | −0.0053 (9) | −0.0001 (10) |
| C9 | 0.0567 (17) | 0.0430 (15) | 0.0399 (15) | 0.0048 (13) | 0.000 | 0.000 |
| Cl1 | 0.0371 (3) | 0.0610 (3) | 0.0800 (4) | 0.0024 (2) | −0.0162 (3) | 0.0145 (3) |
| Cl2 | 0.0434 (3) | 0.0532 (3) | 0.0891 (5) | −0.0076 (2) | 0.0080 (3) | 0.0055 (3) |
| N1 | 0.0464 (9) | 0.0411 (9) | 0.0397 (9) | 0.0039 (7) | −0.0062 (8) | −0.0015 (8) |
| O1 | 0.0366 (7) | 0.0503 (9) | 0.0639 (10) | −0.0058 (6) | −0.0093 (6) | 0.0124 (7) |
| C1—O1 | 1.331 (2) | C6—C7 | 1.453 (3) |
| C1—C2 | 1.395 (3) | C7—N1 | 1.269 (2) |
| C1—C6 | 1.408 (2) | C7—H4 | 0.9300 |
| C2—C3 | 1.373 (3) | C8—N1 | 1.460 (3) |
| C2—Cl1 | 1.7318 (19) | C8—C9 | 1.517 (3) |
| C3—C4 | 1.387 (3) | C8—H5A | 0.9700 |
| C3—H9 | 0.9300 | C8—H5B | 0.9700 |
| C4—C5 | 1.362 (3) | C9—C8i | 1.517 (3) |
| C4—Cl2 | 1.741 (2) | C9—H6A | 0.9700 |
| C5—C6 | 1.395 (3) | C9—H6B | 0.9700 |
| C5—H2 | 0.9300 | O1—H1 | 0.8200 |
| O1—C1—C2 | 119.98 (16) | N1—C7—C6 | 121.61 (17) |
| O1—C1—C6 | 122.23 (17) | N1—C7—H4 | 119.2 |
| C2—C1—C6 | 117.79 (17) | C6—C7—H4 | 119.2 |
| C3—C2—C1 | 122.02 (17) | N1—C8—C9 | 109.52 (18) |
| C3—C2—Cl1 | 119.06 (15) | N1—C8—H5A | 109.8 |
| C1—C2—Cl1 | 118.92 (15) | C9—C8—H5A | 109.8 |
| C2—C3—C4 | 118.75 (19) | N1—C8—H5B | 109.8 |
| C2—C3—H9 | 120.6 | C9—C8—H5B | 109.8 |
| C4—C3—H9 | 120.6 | H5A—C8—H5B | 108.2 |
| C5—C4—C3 | 121.42 (18) | C8i—C9—C8 | 114.1 (3) |
| C5—C4—Cl2 | 120.22 (15) | C8i—C9—H6A | 108.7 |
| C3—C4—Cl2 | 118.35 (16) | C8—C9—H6A | 108.7 |
| C4—C5—C6 | 119.90 (17) | C8i—C9—H6B | 108.7 |
| C4—C5—H2 | 120.1 | C8—C9—H6B | 108.7 |
| C6—C5—H2 | 120.1 | H6A—C9—H6B | 107.6 |
| C5—C6—C1 | 120.07 (18) | C7—N1—C8 | 119.53 (17) |
| C5—C6—C7 | 119.82 (17) | C1—O1—H1 | 109.5 |
| C1—C6—C7 | 120.10 (18) | ||
| O1—C1—C2—C3 | −177.41 (19) | C4—C5—C6—C7 | 179.60 (17) |
| C6—C1—C2—C3 | 2.7 (3) | O1—C1—C6—C5 | 177.77 (18) |
| O1—C1—C2—Cl1 | 2.0 (2) | C2—C1—C6—C5 | −2.4 (3) |
| C6—C1—C2—Cl1 | −177.84 (15) | O1—C1—C6—C7 | −1.3 (3) |
| C1—C2—C3—C4 | −1.2 (3) | C2—C1—C6—C7 | 178.59 (16) |
| Cl1—C2—C3—C4 | 179.35 (16) | C5—C6—C7—N1 | −173.18 (19) |
| C2—C3—C4—C5 | −0.7 (3) | C1—C6—C7—N1 | 5.9 (3) |
| C2—C3—C4—Cl2 | 178.41 (15) | N1—C8—C9—C8i | −174.57 (19) |
| C3—C4—C5—C6 | 1.0 (3) | C6—C7—N1—C8 | 176.32 (17) |
| Cl2—C4—C5—C6 | −178.09 (15) | C9—C8—N1—C7 | −97.64 (19) |
| C4—C5—C6—C1 | 0.5 (3) |
| Symmetry code: (i) −x, −y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.82 | 1.84 | 2.574 (2) | 147 |
| C5—H2···O1ii | 0.93 | 2.43 | 3.336 (2) | 166 |
| C8—H5B···Cl1iii | 0.97 | 2.89 | 3.851 (2) | 169 |
| Symmetry codes: (ii) x+1/4, −y+1/4, z+1/4; (iii) x+1/4, −y+1/4, z+5/4. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.82 | 1.84 | 2.574 (2) | 147 |
| C5—H2···O1i | 0.93 | 2.43 | 3.336 (2) | 166 |
| C8—H5B···Cl1ii | 0.97 | 2.89 | 3.851 (2) | 169 |
| Symmetry codes: (i) x+1/4, −y+1/4, z+1/4; (ii) x+1/4, −y+1/4, z+5/4. |
HK and AAA thank PNU for financial support. MNT thanks GC University of Sargodha, Pakistan for the research facility.
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In continuation of our work on the crystal structure analyses of Schiff base ligands (Kargar et al., (2011); Kia et al., (2010), we synthesized the title compound and report herein on its crystal structure.
The title compound, Fig. 1, a potential tetradentate Schiff base ligand, possesses two-fold rotation symmetry, atom C9 is located on the 2-fold axis. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. The two symmetry related benzene rings are inclined to one another by 80.17 (10) °. There are two intramolecular O—H···N hydrogen bonds which make S(6) ring motifs (Table 1; Bernstein et al., 1995).
In the crystal, molecules are linked by C—H···O and weak C—H···Cl interactions to form a three-dimensional network (Table 1 and Fig. 2).