(E)-4-Chloro-N-[4-(methyl­sulfon­yl)benzyl­idene]aniline

Chen, Y.-H.; Wang, F.; Li, G.-Q.; Qian, S.-S.

doi:10.1107/S160053681105361X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o166

doi:10.1107/S160053681105361X

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(E)-4-Chloro-N-[4-(methylsulfonyl)benzylidene]aniline

Yue-Hu Chen,^a Fang Wang,^a Guo-Qiang Li ^a and Shao-Song Qian ^a ^*

^aSchool of Life Sciences, ShanDong University of Technology, ZiBo 255049, People's Republic of China
^*Correspondence e-mail: njuqss@yahoo.com.cn

(Received 26 November 2011; accepted 13 December 2011; online 17 December 2011)

In the crystal structure of the title compound, C₁₄H₁₂ClNO₂S, the molecules display a trans conformation with respect to the C=N double bond. The dihedral angle between the methylsulfonyl benzene and chlorobenzene rings is 59.59 (8)°. The crystal packing is stabilized by weak C—H⋯O interactions and by π–π stacking interactions between inversion-related methylsulfonyl benzene rings [centroid–centroid distance = 3.8579 (11) Å].

Related literature

For background to the pharmacological properties of Schiff base compounds, see: Villar et al. (2004 ); Pandey et al. (1999 ); Singh & Dash (1988 ). For related structures, see: Qian & Cui (2009 ); Qian & Liu (2010 ).

Experimental

Crystal data

C₁₄H₁₂ClNO₂S
M_r = 293.77
Monoclinic, P 2₁ /n
a = 8.6206 (10) Å
b = 8.8748 (10) Å
c = 17.799 (2) Å
β = 94.972 (1)°
V = 1356.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 296 K
0.25 × 0.23 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.898, T_max = 0.913
11492 measured reflections
3320 independent reflections
2596 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.110
S = 1.04
3320 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.56	3.126 (2)	120
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681105361X/pk2372sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681105361X/pk2372Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681105361X/pk2372Isup3.cml

checkCIF report

Comment top

Schiff base compounds have been of great interest for many years due to their wide range of biological activities. They have been reported to possess pharmacological activity, including anticancer (Villar et al., 2004), antibacterial (Pandey et al., 1999), and antifungal (Singh & Dash, 1988) properties. As an extension of our work on structural characterization of Schiff base compounds, we report here the crystal structure of the title compound (Fig. 1). All bond lengths are comparable to the values observed in closely related compounds (Qian & Cui, 2009; Qian & Liu, 2010). The title compound displays a trans-configuration with respect to the C=N double bond. The dihedral angle between the methylsulfonyl benzene and chlorobenzene rings is 59.59 (8)°. The crystal packing (Fig. 2) is stabilized by weak C—H···O interactions and by π-π stacking interactions of inversion-related (1-x, 1-y, 2-z) methylsulfonyl benzene rings [centroid-centroid distance = 3.8579 (11)Å].

Related literature top

For background to the pharmacological properties of Schiff base compounds, see: Villar et al. (2004); Pandey et al. (1999); Singh & Dash (1988). For related structures, see: Qian & Cui (2009); Qian & Liu (2010).

Experimental top

4-(Methylsulfonyl)benzaldehyde (0.184 g) and 4-chloroaniline (0.114 g) were dissolved in acetonitrile (20 ml). The mixture was stirred at room temperature for 15 min to give a clear yellow solution. After sitting for 5 days exposed to air, yellow block-shaped crystals were obtained at the bottom of the vessel.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram for the title compound, viewed down the a axis.

(E)-4-Chloro-N-[4-(methylsulfonyl)benzylidene]aniline top

Crystal data top

C₁₄H₁₂ClNO₂S	F(000) = 608
M_r = 293.77	D_x = 1.438 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3320 reflections
a = 8.6206 (10) Å	θ = 2.3–28.3°
b = 8.8748 (10) Å	µ = 0.43 mm⁻¹
c = 17.799 (2) Å	T = 296 K
β = 94.972 (1)°	Block, yellow
V = 1356.6 (3) Å³	0.25 × 0.23 × 0.21 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3320 independent reflections
Radiation source: fine-focus sealed tube	2596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→9
T_min = 0.898, T_max = 0.913	k = −11→11
11492 measured reflections	l = −23→23

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0507P)² + 0.4568P] where P = (F_o² + 2F_c²)/3
3320 reflections	(Δ/σ)_max = 0.002
173 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₄H₁₂ClNO₂S	V = 1356.6 (3) Å³
M_r = 293.77	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.6206 (10) Å	µ = 0.43 mm⁻¹
b = 8.8748 (10) Å	T = 296 K
c = 17.799 (2) Å	0.25 × 0.23 × 0.21 mm
β = 94.972 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3320 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2596 reflections with I > 2σ(I)
T_min = 0.898, T_max = 0.913	R_int = 0.040
11492 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.04	Δρ_max = 0.29 e Å⁻³
3320 reflections	Δρ_min = −0.40 e Å⁻³
173 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cl1	1.44038 (7)	0.87940 (7)	0.77377 (3)	0.06397 (19)
S1	0.25645 (5)	0.66162 (5)	1.12920 (2)	0.03972 (14)
O1	0.12146 (16)	0.67285 (18)	1.07669 (8)	0.0580 (4)
O2	0.27398 (19)	0.52896 (17)	1.17454 (9)	0.0644 (4)
N1	0.85437 (18)	0.84443 (17)	0.92329 (9)	0.0414 (3)
C1	1.2692 (2)	0.8676 (2)	0.81840 (10)	0.0403 (4)
C2	1.1903 (2)	0.7325 (2)	0.81801 (10)	0.0431 (4)
H2	1.2286	0.6487	0.7943	0.052*
C3	1.0540 (2)	0.7226 (2)	0.85314 (10)	0.0407 (4)
H3	1.0004	0.6316	0.8532	0.049*
C4	0.9963 (2)	0.84819 (19)	0.88855 (9)	0.0370 (4)
C5	1.0771 (2)	0.9831 (2)	0.88774 (10)	0.0431 (4)
H5	1.0384	1.0679	0.9105	0.052*
C6	1.2147 (2)	0.9930 (2)	0.85339 (11)	0.0447 (4)
H6	1.2697	1.0832	0.8539	0.054*
C7	0.8294 (2)	0.7307 (2)	0.96360 (9)	0.0386 (4)
H7	0.9046	0.6554	0.9693	0.046*
C8	0.68621 (19)	0.71368 (19)	1.00167 (9)	0.0358 (4)
C9	0.6839 (2)	0.6093 (2)	1.05955 (11)	0.0475 (4)
H9	0.7711	0.5498	1.0722	0.057*
C10	0.5532 (2)	0.5927 (2)	1.09869 (11)	0.0465 (4)
H10	0.5526	0.5232	1.1378	0.056*
C11	0.42363 (19)	0.68041 (18)	1.07919 (9)	0.0350 (3)
C12	0.4227 (2)	0.7835 (2)	1.02035 (10)	0.0434 (4)
H12	0.3342	0.8404	1.0067	0.052*
C13	0.5543 (2)	0.8005 (2)	0.98253 (10)	0.0431 (4)
H13	0.5551	0.8708	0.9438	0.052*
C14	0.2630 (3)	0.8207 (2)	1.18768 (12)	0.0544 (5)
H14A	0.1760	0.8191	1.2179	0.082*
H14B	0.2586	0.9102	1.1572	0.082*
H14C	0.3582	0.8201	1.2200	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0498 (3)	0.0688 (4)	0.0779 (4)	−0.0003 (2)	0.0313 (3)	0.0035 (3)
S1	0.0346 (2)	0.0412 (2)	0.0442 (2)	−0.00697 (17)	0.00761 (17)	−0.00031 (17)
O1	0.0350 (7)	0.0783 (10)	0.0600 (8)	−0.0089 (7)	0.0000 (6)	−0.0115 (7)
O2	0.0652 (10)	0.0534 (9)	0.0780 (10)	−0.0046 (7)	0.0263 (8)	0.0217 (8)
N1	0.0337 (8)	0.0431 (8)	0.0484 (8)	−0.0006 (6)	0.0101 (6)	−0.0019 (6)
C1	0.0345 (9)	0.0471 (10)	0.0403 (9)	0.0007 (7)	0.0079 (7)	0.0022 (7)
C2	0.0439 (10)	0.0415 (9)	0.0452 (9)	0.0039 (8)	0.0104 (8)	−0.0045 (8)
C3	0.0399 (10)	0.0380 (9)	0.0447 (9)	−0.0031 (7)	0.0065 (7)	−0.0027 (7)
C4	0.0315 (9)	0.0407 (9)	0.0389 (8)	0.0007 (7)	0.0037 (7)	−0.0004 (7)
C5	0.0433 (10)	0.0391 (9)	0.0479 (10)	0.0000 (7)	0.0102 (8)	−0.0064 (7)
C6	0.0448 (10)	0.0403 (9)	0.0498 (10)	−0.0082 (8)	0.0093 (8)	−0.0007 (8)
C7	0.0324 (9)	0.0427 (9)	0.0406 (8)	0.0014 (7)	0.0033 (7)	−0.0034 (7)
C8	0.0331 (9)	0.0368 (8)	0.0377 (8)	−0.0001 (7)	0.0046 (7)	−0.0026 (7)
C9	0.0393 (10)	0.0498 (11)	0.0540 (11)	0.0126 (8)	0.0065 (8)	0.0127 (8)
C10	0.0436 (10)	0.0471 (10)	0.0496 (10)	0.0074 (8)	0.0090 (8)	0.0161 (8)
C11	0.0323 (8)	0.0356 (8)	0.0371 (8)	−0.0016 (6)	0.0037 (6)	0.0003 (6)
C12	0.0333 (9)	0.0470 (10)	0.0500 (10)	0.0062 (7)	0.0047 (7)	0.0123 (8)
C13	0.0387 (9)	0.0458 (10)	0.0451 (9)	0.0040 (7)	0.0060 (7)	0.0130 (8)
C14	0.0500 (12)	0.0614 (13)	0.0531 (11)	−0.0075 (9)	0.0120 (9)	−0.0155 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.7389 (18)	C6—H6	0.9300
S1—O2	1.4281 (15)	C7—C8	1.467 (2)
S1—O1	1.4315 (15)	C7—H7	0.9300
S1—C14	1.752 (2)	C8—C9	1.387 (2)
S1—C11	1.7662 (17)	C8—C13	1.391 (2)
N1—C7	1.267 (2)	C9—C10	1.383 (3)
N1—C4	1.418 (2)	C9—H9	0.9300
C1—C2	1.377 (3)	C10—C11	1.381 (3)
C1—C6	1.378 (3)	C10—H10	0.9300
C2—C3	1.382 (2)	C11—C12	1.390 (2)
C2—H2	0.9300	C12—C13	1.377 (2)
C3—C4	1.393 (2)	C12—H12	0.9300
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.386 (2)	C14—H14A	0.9600
C5—C6	1.384 (3)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600

O2—S1—O1	117.81 (10)	N1—C7—H7	118.8
O2—S1—C14	109.41 (11)	C8—C7—H7	118.8
O1—S1—C14	108.32 (10)	C9—C8—C13	119.20 (16)
O2—S1—C11	108.16 (9)	C9—C8—C7	118.61 (15)
O1—S1—C11	108.49 (8)	C13—C8—C7	122.18 (15)
C14—S1—C11	103.73 (9)	C10—C9—C8	120.66 (17)
C7—N1—C4	117.42 (15)	C10—C9—H9	119.7
C2—C1—C6	121.20 (17)	C8—C9—H9	119.7
C2—C1—Cl1	119.21 (14)	C11—C10—C9	119.35 (16)
C6—C1—Cl1	119.59 (14)	C11—C10—H10	120.3
C1—C2—C3	119.48 (16)	C9—C10—H10	120.3
C1—C2—H2	120.3	C10—C11—C12	120.79 (16)
C3—C2—H2	120.3	C10—C11—S1	119.85 (13)
C2—C3—C4	120.29 (16)	C12—C11—S1	119.36 (13)
C2—C3—H3	119.9	C13—C12—C11	119.31 (16)
C4—C3—H3	119.9	C13—C12—H12	120.3
C5—C4—C3	119.17 (16)	C11—C12—H12	120.3
C5—C4—N1	118.56 (15)	C12—C13—C8	120.67 (16)
C3—C4—N1	122.23 (15)	C12—C13—H13	119.7
C6—C5—C4	120.69 (17)	C8—C13—H13	119.7
C6—C5—H5	119.7	S1—C14—H14A	109.5
C4—C5—H5	119.7	S1—C14—H14B	109.5
C1—C6—C5	119.14 (17)	H14A—C14—H14B	109.5
C1—C6—H6	120.4	S1—C14—H14C	109.5
C5—C6—H6	120.4	H14A—C14—H14C	109.5
N1—C7—C8	122.31 (16)	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.56	3.126 (2)	120

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂ClNO₂S
M_r	293.77
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	8.6206 (10), 8.8748 (10), 17.799 (2)
β (°)	94.972 (1)
V (Å³)	1356.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.25 × 0.23 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.898, 0.913
No. of measured, independent and observed [I > 2σ(I)] reflections	11492, 3320, 2596
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.110, 1.04
No. of reflections	3320
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.40

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.56	3.126 (2)	119.6

Symmetry code: (i) x+1, y, z.

Acknowledgements

This project was sponsored by the ShanDong Province Science & Technology Innovation Foundation (People's Republic of China).

References

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