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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2583.
Published online 2010 September 18. doi:  10.1107/S1600536810036640
PMCID: PMC2983430

N-[(E)-2,4-Dichloro­benzyl­idene]-4-methyl­aniline

Abstract

In the title compound, C14H11Cl2N, the dihedral angle between the 4-methyl­anilinic and 2,4-dichloro­benzaldehyde moieties is 7.37 (8)°. In the crystal, C—H(...)π inter­actions between the terminal methyl group and a symmetry-related ring of the anilinic group help to establish the packing.

Related literature

For background to our project to synthesize various Schiff bases of 2,4-dichloro­benzaldehyde as possible ligands for complexing metals, see: Hayat et al. (2010 [triangle]). For related structures, see: Hayat et al. (2010 [triangle]); Bernstein (1972 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2583-scheme1.jpg

Experimental

Crystal data

  • C14H11Cl2N
  • M r = 264.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2583-efi1.jpg
  • a = 10.1069 (3) Å
  • b = 4.7469 (2) Å
  • c = 12.9922 (4) Å
  • β = 95.668 (2)°
  • V = 620.27 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.50 mm−1
  • T = 296 K
  • 0.32 × 0.20 × 0.18 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.886, T max = 0.916
  • 5221 measured reflections
  • 2082 independent reflections
  • 1937 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.079
  • S = 1.06
  • 2082 reflections
  • 155 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.15 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 807 Friedel pairs
  • Flack parameter: 0.10 (7)

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036640/dn2602sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036640/dn2602Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

As a part of our on going project related to synthesize various Schiff bases of 2,4-dichlorobenzaldehyde as possible ligands for complexing metals (Hayat et al., 2010), we report here the title compound.

In the title compound, the 4-methylanilinic group A (C1—C7/N1) and 2,4-dichlorobenzaldehyde moiety B (C8—C14/CL1/CL2) are planar with r. m. s. deviation of 0.0114 and 0.0209 Å, respectively. The dihedral angle between A/B is 7.37 (8)°. The title compound essentially consists of monomers (Fig. 1). There exist weak intramolecular C—H···Cl hydrogen bonds (Table 1, Fig. 1) forming an S(5) ring motif (Bernstein et al., 1995). There also exists a C—H···π interaction (Table 1) which helps in consolidating the crystal packing. Bond distances and bond angles agree with related compounds already published as the 4-chloro-N-[(E)-2,4-dichlorobenzylidene]aniline (Hayat et al., 2010) and the N-(2,4-dichlorobenzylidene)aniline (Bernstein, 1972).

Experimental

Equimolar quantities of 4-methylaniline and 2,4-dichlorobanzaldehyde were refluxed in methanol for 30 min resulting in yellow solution. The solution was kept at room temperature which affoarded light yellow needles after 72 h.

Refinement

The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H-atoms and x = 1.2 for aryl H-atoms.

Figures

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 circles of arbitrary radii. The dotted line represents the intramolecular H-bonding.

Crystal data

C14H11Cl2NF(000) = 272
Mr = 264.14Dx = 1.414 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1937 reflections
a = 10.1069 (3) Åθ = 1.6–25.2°
b = 4.7469 (2) ŵ = 0.50 mm1
c = 12.9922 (4) ÅT = 296 K
β = 95.668 (2)°Needles, colorless
V = 620.27 (4) Å30.32 × 0.20 × 0.18 mm
Z = 2

Data collection

Bruker Kappa APEXII CCD diffractometer2082 independent reflections
Radiation source: fine-focus sealed tube1937 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 8.20 pixels mm-1θmax = 25.2°, θmin = 1.6°
ω scansh = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −5→4
Tmin = 0.886, Tmax = 0.916l = −15→15
5221 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.079w = 1/[σ2(Fo2) + (0.0434P)2 + 0.0661P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2082 reflectionsΔρmax = 0.16 e Å3
155 parametersΔρmin = −0.14 e Å3
1 restraintAbsolute structure: Flack (1983), 807 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.10 (7)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl1−0.16693 (6)0.51040 (18)0.89821 (4)0.0670 (3)
Cl2−0.39799 (5)1.07125 (13)0.57256 (4)0.0492 (2)
N10.08154 (17)0.0949 (5)0.69281 (13)0.0393 (6)
C10.1724 (2)−0.1021 (5)0.74152 (15)0.0359 (7)
C20.2670 (2)−0.2162 (5)0.68218 (17)0.0436 (8)
C30.3592 (2)−0.4089 (6)0.72278 (18)0.0488 (8)
C40.3619 (2)−0.4993 (5)0.82462 (16)0.0422 (8)
C50.2663 (2)−0.3948 (6)0.88216 (16)0.0478 (8)
C60.1728 (2)−0.1997 (6)0.84251 (16)0.0450 (8)
C70.4635 (3)−0.7104 (6)0.8693 (2)0.0601 (10)
C80.0090 (2)0.2361 (5)0.74719 (16)0.0396 (7)
C9−0.08867 (19)0.4437 (5)0.70395 (15)0.0354 (6)
C10−0.17493 (19)0.5787 (6)0.76574 (14)0.0394 (6)
C11−0.2697 (2)0.7695 (5)0.72713 (16)0.0408 (7)
C12−0.2778 (2)0.8341 (5)0.62295 (16)0.0359 (7)
C13−0.1920 (2)0.7130 (5)0.55900 (15)0.0376 (7)
C14−0.10045 (19)0.5191 (5)0.59983 (14)0.0378 (7)
H20.26757−0.160570.613590.0523*
H30.42111−0.480340.681210.0586*
H50.26408−0.456860.949870.0574*
H60.10958−0.133130.883900.0540*
H7A0.45868−0.726130.942460.0901*
H7B0.55083−0.648720.856420.0901*
H7C0.44563−0.890530.837300.0901*
H80.017850.207230.818330.0475*
H11−0.326890.852790.770040.0490*
H13−0.196210.762120.489460.0452*
H14−0.044260.434960.556320.0453*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0692 (4)0.0965 (7)0.0371 (3)0.0234 (4)0.0140 (3)0.0138 (3)
Cl20.0445 (3)0.0449 (4)0.0571 (3)0.0089 (3)−0.0002 (2)0.0058 (3)
N10.0421 (9)0.0365 (12)0.0392 (8)0.0048 (9)0.0034 (7)0.0005 (9)
C10.0374 (11)0.0300 (13)0.0394 (11)0.0005 (9)−0.0007 (8)−0.0031 (9)
C20.0509 (13)0.0423 (15)0.0388 (11)0.0090 (12)0.0108 (10)0.0015 (10)
C30.0487 (12)0.0460 (15)0.0524 (12)0.0099 (14)0.0083 (10)−0.0053 (13)
C40.0413 (12)0.0301 (15)0.0529 (12)−0.0007 (10)−0.0063 (9)−0.0033 (11)
C50.0565 (13)0.0481 (17)0.0373 (10)0.0021 (13)−0.0029 (9)0.0031 (11)
C60.0497 (13)0.0473 (15)0.0384 (11)0.0087 (12)0.0062 (9)−0.0025 (10)
C70.0529 (15)0.0483 (17)0.0748 (18)0.0085 (13)−0.0145 (12)0.0017 (14)
C80.0419 (12)0.0385 (14)0.0380 (10)0.0012 (10)0.0026 (9)0.0012 (10)
C90.0330 (10)0.0335 (12)0.0394 (10)−0.0025 (10)0.0016 (8)−0.0012 (10)
C100.0415 (10)0.0443 (14)0.0328 (9)−0.0009 (12)0.0057 (8)0.0030 (11)
C110.0399 (11)0.0410 (15)0.0424 (11)0.0039 (10)0.0089 (9)−0.0022 (10)
C120.0352 (11)0.0290 (12)0.0426 (11)−0.0022 (9)−0.0004 (8)0.0011 (9)
C130.0419 (12)0.0360 (13)0.0348 (10)−0.0011 (10)0.0027 (9)−0.0014 (10)
C140.0370 (10)0.0388 (15)0.0378 (10)0.0020 (10)0.0055 (8)−0.0060 (11)

Geometric parameters (Å, °)

Cl1—C101.7454 (19)C11—C121.382 (3)
Cl2—C121.736 (2)C12—C131.384 (3)
N1—C11.415 (3)C13—C141.374 (3)
N1—C81.260 (3)C2—H20.9300
C1—C21.396 (3)C3—H30.9300
C1—C61.391 (3)C5—H50.9300
C2—C31.373 (3)C6—H60.9300
C3—C41.389 (3)C7—H7A0.9600
C4—C51.372 (3)C7—H7B0.9600
C4—C71.509 (4)C7—H7C0.9600
C5—C61.386 (3)C8—H80.9300
C8—C91.467 (3)C11—H110.9300
C9—C101.398 (3)C13—H130.9300
C9—C141.393 (3)C14—H140.9300
C10—C111.376 (3)
Cl1···C6i3.519 (2)C1···H7Cviii3.0800
Cl2···Cl2ii3.5598 (8)C2···H7Cviii3.0000
Cl2···Cl2iii3.5598 (8)C3···H7Cviii2.9600
Cl1···H7Biv2.9500C4···H7Cviii3.0100
Cl1···H6i2.9100C5···H7Cviii3.0900
Cl1···H82.6500C6···H82.4900
Cl2···H2v3.1400C8···H62.6300
N1···C14vi3.446 (3)C13···H2x2.9000
N1···H142.6300H2···Cl2xi3.1400
N1···H13vii2.8500H2···C13vii2.9000
C1···C4viii3.552 (3)H2···H13vii2.4800
C1···C8vi3.553 (3)H5···H7A2.3600
C1···C9vi3.405 (3)H6···C82.6300
C4···C1vi3.552 (3)H6···H82.0100
C5···C8vi3.465 (3)H6···Cl1ix2.9100
C6···C9vi3.486 (3)H7A···H52.3600
C6···C8vi3.323 (3)H7B···Cl1xii2.9500
C6···Cl1ix3.519 (2)H7C···C1vi3.0800
C8···C6viii3.323 (3)H7C···C2vi3.0000
C8···C1viii3.553 (3)H7C···C3vi2.9600
C8···C5viii3.465 (3)H7C···C4vi3.0100
C8···C11vi3.573 (3)H7C···C5vi3.0900
C9···C6viii3.486 (3)H8···Cl12.6500
C9···C1viii3.405 (3)H8···C62.4900
C9···C12vi3.569 (3)H8···H62.0100
C11···C8viii3.573 (3)H13···N1x2.8500
C12···C9viii3.569 (3)H13···H2x2.4800
C14···N1viii3.446 (3)H14···N12.6300
C1—N1—C8119.23 (18)C9—C14—C13122.46 (19)
N1—C1—C2117.33 (18)C1—C2—H2119.00
N1—C1—C6125.67 (19)C3—C2—H2119.00
C2—C1—C6117.0 (2)C2—C3—H3119.00
C1—C2—C3121.5 (2)C4—C3—H3119.00
C2—C3—C4121.4 (2)C4—C5—H5119.00
C3—C4—C5117.3 (2)C6—C5—H5119.00
C3—C4—C7121.4 (2)C1—C6—H6120.00
C5—C4—C7121.3 (2)C5—C6—H6120.00
C4—C5—C6122.0 (2)C4—C7—H7A109.00
C1—C6—C5120.8 (2)C4—C7—H7B109.00
N1—C8—C9123.32 (19)C4—C7—H7C109.00
C8—C9—C10121.49 (18)H7A—C7—H7B110.00
C8—C9—C14122.30 (19)H7A—C7—H7C110.00
C10—C9—C14116.21 (19)H7B—C7—H7C109.00
Cl1—C10—C9120.69 (17)N1—C8—H8118.00
Cl1—C10—C11116.39 (16)C9—C8—H8118.00
C9—C10—C11122.92 (18)C10—C11—H11121.00
C10—C11—C12118.33 (19)C12—C11—H11121.00
Cl2—C12—C11118.99 (16)C12—C13—H13121.00
Cl2—C12—C13119.97 (16)C14—C13—H13120.00
C11—C12—C13121.0 (2)C9—C14—H14119.00
C12—C13—C14118.98 (18)C13—C14—H14119.00
C8—N1—C1—C2−168.7 (2)N1—C8—C9—C14−5.9 (4)
C8—N1—C1—C613.7 (4)C8—C9—C10—Cl11.5 (3)
C1—N1—C8—C9−179.6 (2)C8—C9—C10—C11−178.5 (2)
N1—C1—C2—C3−180.0 (2)C14—C9—C10—Cl1−178.14 (17)
C6—C1—C2—C3−2.2 (3)C14—C9—C10—C112.0 (3)
N1—C1—C6—C5179.6 (2)C8—C9—C14—C13179.9 (2)
C2—C1—C6—C52.0 (3)C10—C9—C14—C13−0.6 (3)
C1—C2—C3—C40.2 (4)Cl1—C10—C11—C12178.75 (18)
C2—C3—C4—C51.9 (4)C9—C10—C11—C12−1.3 (4)
C2—C3—C4—C7−179.8 (2)C10—C11—C12—Cl2179.26 (18)
C3—C4—C5—C6−2.1 (4)C10—C11—C12—C13−0.7 (3)
C7—C4—C5—C6179.6 (2)Cl2—C12—C13—C14−177.94 (17)
C4—C5—C6—C10.2 (4)C11—C12—C13—C142.1 (3)
N1—C8—C9—C10174.6 (2)C12—C13—C14—C9−1.4 (3)

Symmetry codes: (i) −x, y+1/2, −z+2; (ii) −x−1, y−1/2, −z+1; (iii) −x−1, y+1/2, −z+1; (iv) x−1, y+1, z; (v) −x, y+3/2, −z+1; (vi) x, y−1, z; (vii) −x, y−1/2, −z+1; (viii) x, y+1, z; (ix) −x, y−1/2, −z+2; (x) −x, y+1/2, −z+1; (xi) −x, y−3/2, −z+1; (xii) x+1, y−1, z.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 phenyl ring.
D—H···AD—HH···AD···AD—H···A
C8—H8···Cl10.932.653.065 (2)108
C7—H7C···Cg1vi0.962.713.565 (2)148

Symmetry codes: (vi) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2602).

References

  • Bernstein, J. (1972). J. Chem. Soc. Perkin Trans. 2, pp. 946–950.
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Hayat, U., Siddiqui, W. A., Tahir, M. N. & Hussain, G. (2010). Acta Cryst. E66, o2523. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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