Acta Cryst. (2010). E66, o2523 [ doi:10.1107/S1600536810035774 ]
In the molecule of the title compound, C13H8Cl3N, the 4-chloroaniline and 2,4-dichlorobenzaldehyde moieties are planar with r.m.s. deviation of 0.0115 and 0.0116 Å, respectively, and are oriented at a dihedral angle of 13.94 (8)°.
An equimolar ratio of 2,4-dichlorobanzaldehyde and 4-chloroaniline were refluxed in xylene (20 ml) with acetic acid (2 ml) as a catalyst for an hour. The completion of the reaction was monitored through TLC. After completion of the reaction, the xylene was distilled out and the solid product obtained was dried. The dried crude material obtained was recrystallized in ethyl acetate and methanol (1:1 v/v) to affoard light pink needles of the title compound in 24 h.
The H-atoms were positioned geometrically (C–H = 0.93 Å) and were included in the refinement in the riding model approximation, with with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
![[Figure 1]](./rz2483fig1thm.gif)
| Fig. 1. View of the title compound with the atom numbering scheme. The thermal ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii. The dotted line represent the intramolecular H-bonds. |
| C13H8Cl3N | F(000) = 576 |
| Mr = 284.55 | Dx = 1.528 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1372 reflections |
| a = 3.9665 (3) Å | θ = 2.0–25.2° |
| b = 27.639 (2) Å | µ = 0.71 mm−1 |
| c = 11.4287 (9) Å | T = 296 K |
| β = 99.165 (3)° | Needles, light pink |
| V = 1236.93 (16) Å3 | 0.32 × 0.12 × 0.08 mm |
| Z = 4 |
| Bruker Kappa APEXII CCD diffractometer | 2239 independent reflections |
| Radiation source: fine-focus sealed tube | 1372 reflections with I > 2σ(I) |
| graphite | Rint = 0.047 |
| Detector resolution: 8.10 pixels mm-1 | θmax = 25.2°, θmin = 2.0° |
| ω scans | h = −4→4 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −32→33 |
| Tmin = 0.903, Tmax = 0.946 | l = −13→13 |
| 9236 measured reflections |
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.107 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.032P)2 + 0.7441P] where P = (Fo2 + 2Fc2)/3 |
| 2239 reflections | (Δ/σ)max < 0.001 |
| 154 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
| C13H8Cl3N | V = 1236.93 (16) Å3 |
| Mr = 284.55 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 3.9665 (3) Å | µ = 0.71 mm−1 |
| b = 27.639 (2) Å | T = 296 K |
| c = 11.4287 (9) Å | 0.32 × 0.12 × 0.08 mm |
| β = 99.165 (3)° |
| Bruker Kappa APEXII CCD diffractometer | 2239 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1372 reflections with I > 2σ(I) |
| Tmin = 0.903, Tmax = 0.946 | Rint = 0.047 |
| 9236 measured reflections | θmax = 25.2° |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.107 | Δρmax = 0.20 e Å−3 |
| S = 1.02 | Δρmin = −0.21 e Å−3 |
| 2239 reflections | Absolute structure: ? |
| 154 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | −0.1794 (3) | 0.20049 (4) | −0.09024 (9) | 0.0739 (4) | |
| Cl2 | 1.1913 (3) | 0.18426 (3) | 0.60890 (9) | 0.0635 (4) | |
| Cl3 | 1.3135 (3) | 0.02321 (4) | 0.87154 (8) | 0.0702 (4) | |
| N1 | 0.4889 (7) | 0.10444 (10) | 0.3494 (2) | 0.0458 (10) | |
| C1 | 0.3428 (8) | 0.12998 (12) | 0.2462 (3) | 0.0409 (11) | |
| C2 | 0.1799 (9) | 0.10234 (13) | 0.1521 (3) | 0.0521 (14) | |
| C3 | 0.0224 (9) | 0.12381 (14) | 0.0490 (3) | 0.0567 (16) | |
| C4 | 0.0238 (8) | 0.17295 (14) | 0.0389 (3) | 0.0489 (14) | |
| C5 | 0.1799 (9) | 0.20122 (14) | 0.1310 (3) | 0.0576 (14) | |
| C6 | 0.3342 (9) | 0.17971 (14) | 0.2341 (3) | 0.0573 (12) | |
| C7 | 0.7186 (8) | 0.12440 (13) | 0.4242 (3) | 0.0440 (12) | |
| C8 | 0.8657 (7) | 0.10042 (12) | 0.5344 (3) | 0.0383 (11) | |
| C9 | 1.0827 (8) | 0.12398 (12) | 0.6247 (3) | 0.0409 (11) | |
| C10 | 1.2154 (8) | 0.10111 (13) | 0.7292 (3) | 0.0469 (12) | |
| C11 | 1.1380 (8) | 0.05286 (13) | 0.7431 (3) | 0.0469 (14) | |
| C12 | 0.9276 (9) | 0.02799 (13) | 0.6552 (3) | 0.0494 (12) | |
| C13 | 0.7960 (8) | 0.05201 (13) | 0.5530 (3) | 0.0467 (12) | |
| H2 | 0.17733 | 0.06882 | 0.15891 | 0.0624* | |
| H3 | −0.08427 | 0.10490 | −0.01344 | 0.0681* | |
| H5 | 0.18079 | 0.23473 | 0.12349 | 0.0691* | |
| H6 | 0.43465 | 0.19895 | 0.29688 | 0.0683* | |
| H7 | 0.79497 | 0.15515 | 0.40831 | 0.0528* | |
| H10 | 1.35406 | 0.11780 | 0.78919 | 0.0562* | |
| H12 | 0.87615 | −0.00443 | 0.66514 | 0.0591* | |
| H13 | 0.65459 | 0.03524 | 0.49395 | 0.0560* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0774 (7) | 0.0752 (8) | 0.0638 (7) | 0.0095 (6) | −0.0051 (5) | 0.0237 (6) |
| Cl2 | 0.0658 (6) | 0.0420 (6) | 0.0792 (7) | −0.0104 (5) | 0.0009 (5) | 0.0039 (5) |
| Cl3 | 0.0822 (7) | 0.0674 (8) | 0.0552 (6) | 0.0117 (6) | −0.0065 (5) | 0.0141 (5) |
| N1 | 0.0531 (18) | 0.0406 (18) | 0.0431 (16) | 0.0013 (14) | 0.0058 (13) | 0.0019 (14) |
| C1 | 0.0409 (19) | 0.041 (2) | 0.0413 (19) | −0.0013 (16) | 0.0077 (15) | 0.0013 (16) |
| C2 | 0.070 (3) | 0.035 (2) | 0.050 (2) | −0.0030 (18) | 0.0056 (18) | 0.0025 (17) |
| C3 | 0.066 (3) | 0.052 (3) | 0.049 (2) | −0.004 (2) | 0.0000 (18) | −0.0037 (19) |
| C4 | 0.043 (2) | 0.053 (3) | 0.051 (2) | 0.0061 (18) | 0.0088 (16) | 0.0085 (19) |
| C5 | 0.058 (2) | 0.037 (2) | 0.074 (3) | 0.0060 (19) | −0.001 (2) | 0.007 (2) |
| C6 | 0.060 (2) | 0.046 (2) | 0.061 (2) | 0.0027 (19) | −0.0057 (19) | −0.007 (2) |
| C7 | 0.043 (2) | 0.043 (2) | 0.048 (2) | −0.0034 (16) | 0.0137 (16) | 0.0043 (17) |
| C8 | 0.0338 (18) | 0.040 (2) | 0.0417 (19) | 0.0008 (15) | 0.0078 (14) | 0.0022 (16) |
| C9 | 0.0379 (19) | 0.037 (2) | 0.049 (2) | −0.0018 (15) | 0.0105 (15) | −0.0006 (16) |
| C10 | 0.043 (2) | 0.048 (2) | 0.047 (2) | 0.0007 (17) | −0.0011 (15) | −0.0010 (18) |
| C11 | 0.045 (2) | 0.053 (3) | 0.042 (2) | 0.0076 (18) | 0.0049 (16) | 0.0015 (18) |
| C12 | 0.061 (2) | 0.040 (2) | 0.047 (2) | 0.0003 (18) | 0.0084 (17) | 0.0054 (17) |
| C13 | 0.051 (2) | 0.044 (2) | 0.045 (2) | −0.0051 (17) | 0.0074 (16) | −0.0060 (17) |
| Cl1—C4 | 1.740 (4) | C8—C13 | 1.390 (5) |
| Cl2—C9 | 1.738 (3) | C9—C10 | 1.379 (5) |
| Cl3—C11 | 1.728 (4) | C10—C11 | 1.383 (5) |
| N1—C1 | 1.417 (4) | C11—C12 | 1.382 (5) |
| N1—C7 | 1.272 (4) | C12—C13 | 1.372 (5) |
| C1—C2 | 1.392 (5) | C2—H2 | 0.9300 |
| C1—C6 | 1.381 (5) | C3—H3 | 0.9300 |
| C2—C3 | 1.377 (5) | C5—H5 | 0.9300 |
| C3—C4 | 1.363 (5) | C6—H6 | 0.9300 |
| C4—C5 | 1.376 (5) | C7—H7 | 0.9300 |
| C5—C6 | 1.374 (5) | C10—H10 | 0.9300 |
| C7—C8 | 1.460 (5) | C12—H12 | 0.9300 |
| C8—C9 | 1.395 (5) | C13—H13 | 0.9300 |
| Cl2···C7i | 3.602 (4) | C13···C12viii | 3.547 (5) |
| Cl3···Cl3ii | 3.3276 (14) | C13···C10vii | 3.561 (5) |
| Cl1···H6iii | 3.1300 | C6···H7 | 2.5700 |
| Cl1···H10iv | 3.1200 | C7···H6 | 2.6700 |
| Cl2···H5v | 3.0400 | C12···H13viii | 3.1000 |
| Cl2···H5vi | 2.9500 | C13···H13ix | 3.0000 |
| Cl2···H7 | 2.6900 | H5···Cl2x | 2.9500 |
| N1···C7vii | 3.347 (4) | H5···Cl2iii | 3.0400 |
| N1···H13 | 2.5400 | H6···C7 | 2.6700 |
| C1···C7vii | 3.449 (5) | H6···H7 | 2.1300 |
| C7···C1i | 3.449 (5) | H6···Cl1v | 3.1300 |
| C7···Cl2vii | 3.602 (4) | H7···Cl2 | 2.6900 |
| C7···N1i | 3.347 (4) | H7···C6 | 2.5700 |
| C8···C9vii | 3.487 (4) | H7···H6 | 2.1300 |
| C9···C8i | 3.487 (4) | H10···Cl1xi | 3.1200 |
| C10···C13i | 3.561 (5) | H13···N1 | 2.5400 |
| C11···C12i | 3.506 (5) | H13···C12viii | 3.1000 |
| C12···C13viii | 3.547 (5) | H13···C13ix | 3.0000 |
| C12···C11vii | 3.506 (5) | H13···H13ix | 2.3200 |
| C1—N1—C7 | 119.9 (3) | Cl3—C11—C12 | 119.8 (3) |
| N1—C1—C2 | 116.6 (3) | C10—C11—C12 | 121.0 (3) |
| N1—C1—C6 | 125.4 (3) | C11—C12—C13 | 118.8 (3) |
| C2—C1—C6 | 117.9 (3) | C8—C13—C12 | 122.6 (3) |
| C1—C2—C3 | 121.1 (3) | C1—C2—H2 | 119.00 |
| C2—C3—C4 | 119.6 (3) | C3—C2—H2 | 119.00 |
| Cl1—C4—C3 | 120.0 (3) | C2—C3—H3 | 120.00 |
| Cl1—C4—C5 | 119.4 (3) | C4—C3—H3 | 120.00 |
| C3—C4—C5 | 120.6 (3) | C4—C5—H5 | 120.00 |
| C4—C5—C6 | 119.7 (4) | C6—C5—H5 | 120.00 |
| C1—C6—C5 | 121.1 (3) | C1—C6—H6 | 119.00 |
| N1—C7—C8 | 121.9 (3) | C5—C6—H6 | 119.00 |
| C7—C8—C9 | 122.7 (3) | N1—C7—H7 | 119.00 |
| C7—C8—C13 | 120.5 (3) | C8—C7—H7 | 119.00 |
| C9—C8—C13 | 116.8 (3) | C9—C10—H10 | 121.00 |
| Cl2—C9—C8 | 120.3 (3) | C11—C10—H10 | 121.00 |
| Cl2—C9—C10 | 117.6 (3) | C11—C12—H12 | 121.00 |
| C8—C9—C10 | 122.1 (3) | C13—C12—H12 | 121.00 |
| C9—C10—C11 | 118.7 (3) | C8—C13—H13 | 119.00 |
| Cl3—C11—C10 | 119.2 (3) | C12—C13—H13 | 119.00 |
| C7—N1—C1—C2 | 160.2 (3) | N1—C7—C8—C13 | 9.7 (5) |
| C7—N1—C1—C6 | −23.3 (5) | C7—C8—C9—Cl2 | −0.4 (4) |
| C1—N1—C7—C8 | 177.2 (3) | C7—C8—C9—C10 | 178.9 (3) |
| N1—C1—C2—C3 | 178.4 (3) | C13—C8—C9—Cl2 | 178.9 (2) |
| C6—C1—C2—C3 | 1.6 (5) | C13—C8—C9—C10 | −1.8 (5) |
| N1—C1—C6—C5 | −178.6 (3) | C7—C8—C13—C12 | −179.8 (3) |
| C2—C1—C6—C5 | −2.2 (5) | C9—C8—C13—C12 | 0.9 (5) |
| C1—C2—C3—C4 | −0.4 (5) | Cl2—C9—C10—C11 | −178.8 (3) |
| C2—C3—C4—Cl1 | −179.1 (3) | C8—C9—C10—C11 | 1.9 (5) |
| C2—C3—C4—C5 | −0.3 (5) | C9—C10—C11—Cl3 | 177.9 (3) |
| Cl1—C4—C5—C6 | 178.6 (3) | C9—C10—C11—C12 | −1.0 (5) |
| C3—C4—C5—C6 | −0.3 (5) | Cl3—C11—C12—C13 | −178.8 (3) |
| C4—C5—C6—C1 | 1.6 (5) | C10—C11—C12—C13 | 0.1 (5) |
| N1—C7—C8—C9 | −171.0 (3) | C11—C12—C13—C8 | −0.1 (5) |
| Symmetry codes: (i) x+1, y, z; (ii) −x+3, −y, −z+2; (iii) x−1/2, −y+1/2, z−1/2; (iv) x−2, y, z−1; (v) x+1/2, −y+1/2, z+1/2; (vi) x+3/2, −y+1/2, z+1/2; (vii) x−1, y, z; (viii) −x+2, −y, −z+1; (ix) −x+1, −y, −z+1; (x) x−3/2, −y+1/2, z−1/2; (xi) x+2, y, z+1. |
The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. They also acknowledge the technical support provided by Bana International, Karachi, Pakistan.
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The synthesis and crystal structure of the title compound is herein reported as a part of our new project aimed to the study of new Schiff bases of 2,4-dichlorobenzaldehyde and their metal complexation abilities. The crystal structures of the related compounds N-(2,4-dichlorobenzylidene)aniline (Bernstein, 1972) and N-(2,4-dichlorobenzylidene)-N'-phenylhydrazine (Yin et al., 2007) have been already published.
In the title compound (Fig. 1), the 4-chloroaniline (C1—C6/N1/Cl1) and 2,4-dichlorobenzaldehyde (C7—C13/Cl2/Cl3) moieties are planar with r. m. s. deviation of 0.0115 and 0.0116 Å, respectively. The dihedral angle between the two moieties is 13.94 (8)°. There exist a weak intramolecular C—H···Cl hydrogen bond (Table 1, Fig. 1) forming an S(5) ring motif (Bernstein et al., 1995). The crystal structure is stabilized only by van der Waals interactions.