4-Chloro-N-[(E)-2,4-dichloro­benzyl­idene]aniline

Hayat, U.; Siddiqui, W.A.; Tahir, M.N.; Hussain, G.

doi:10.1107/S1600536810035774

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2523

doi:10.1107/S1600536810035774

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4-Chloro-N-[(E)-2,4-dichlorobenzylidene]aniline

Umar Hayat,^a Waseeq Ahmad Siddiqui,^a M. Nawaz Tahir ^b ^* and Ghulam Hussain ^a

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 29 August 2010; accepted 6 September 2010; online 11 September 2010)

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)°.

Related literature

For related structures, see: Bernstein (1972 ), Yin et al. (2007 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₈Cl₃N
M_r = 284.55
Monoclinic, P 2₁ /n
a = 3.9665 (3) Å
b = 27.639 (2) Å
c = 11.4287 (9) Å
β = 99.165 (3)°
V = 1236.93 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 296 K
0.32 × 0.12 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.903, T_max = 0.946
9236 measured reflections
2239 independent reflections
1372 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.107
S = 1.02
2239 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035774/rz2483sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035774/rz2483Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For related structures, see: Bernstein (1972), Yin et al. (2007). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

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.

Computing details top

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).

Figures top

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.

4-Chloro-N-[(E)-2,4-dichlorobenzylidene]aniline top

Crystal data top

C₁₃H₈Cl₃N	F(000) = 576
M_r = 284.55	D_x = 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

Data collection top

Bruker Kappa APEXII CCD diffractometer	2239 independent reflections
Radiation source: fine-focus sealed tube	1372 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 8.10 pixels mm^-1	θ_max = 25.2°, θ_min = 2.0°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −32→33
T_min = 0.903, T_max = 0.946	l = −13→13
9236 measured reflections

Refinement top

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(F_o²) + (0.032P)² + 0.7441P] where P = (F_o² + 2F_c²)/3
2239 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₃H₈Cl₃N	V = 1236.93 (16) Å³
M_r = 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)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2239 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1372 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.946	R_int = 0.047
9236 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.02	Δρ_max = 0.20 e Å⁻³
2239 reflections	Δρ_min = −0.21 e Å⁻³
154 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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···C12^viii	3.547 (5)
Cl3···Cl3ⁱⁱ	3.3276 (14)	C13···C10^vii	3.561 (5)
Cl1···H6ⁱⁱⁱ	3.1300	C6···H7	2.5700
Cl1···H10^iv	3.1200	C7···H6	2.6700
Cl2···H5^v	3.0400	C12···H13^viii	3.1000
Cl2···H5^vi	2.9500	C13···H13^ix	3.0000
Cl2···H7	2.6900	H5···Cl2^x	2.9500
N1···C7^vii	3.347 (4)	H5···Cl2ⁱⁱⁱ	3.0400
N1···H13	2.5400	H6···C7	2.6700
C1···C7^vii	3.449 (5)	H6···H7	2.1300
C7···C1ⁱ	3.449 (5)	H6···Cl1^v	3.1300
C7···Cl2^vii	3.602 (4)	H7···Cl2	2.6900
C7···N1ⁱ	3.347 (4)	H7···C6	2.5700
C8···C9^vii	3.487 (4)	H7···H6	2.1300
C9···C8ⁱ	3.487 (4)	H10···Cl1^xi	3.1200
C10···C13ⁱ	3.561 (5)	H13···N1	2.5400
C11···C12ⁱ	3.506 (5)	H13···C12^viii	3.1000
C12···C13^viii	3.547 (5)	H13···C13^ix	3.0000
C12···C11^vii	3.506 (5)	H13···H13^ix	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl2	0.93	2.69	3.074 (4)	106

Experimental details

Crystal data
Chemical formula	C₁₃H₈Cl₃N
M_r	284.55
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	3.9665 (3), 27.639 (2), 11.4287 (9)
β (°)	99.165 (3)
V (Å³)	1236.93 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.32 × 0.12 × 0.08

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.903, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	9236, 2239, 1372
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.107, 1.02
No. of reflections	2239
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl2	0.93	2.69	3.074 (4)	106

Acknowledgements

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.

References

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