(2E)-1-(4-Chloro­phen­yl)-3-[4-(methyl­sulfan­yl)phen­yl]prop-2-en-1-one

Harrison, W.T.A.; Yathirajan, H.S.; Narayana, B.; Mithun, A.; Sarojini, B.K.

doi:10.1107/S1600536806037330

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages o5290-o5292

https://doi.org/10.1107/S1600536806037330

(2E)-1-(4-Chlorophenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one

William T. A. Harrison,^a ^* H. S. Yathirajan,^b B. Narayana,^c A. Mithun ^d and B. K. Sarojini ^e

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^cDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, India, ^dDepartment of Chemistry, Mangalore University, Mangalagangotri-574 199, India, and ^eDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 13 September 2006; accepted 13 September 2006; online 27 October 2006)

The geometrical parameters for the title compound, C₁₆H₁₃ClOS, are normal. The dihedral angle between the two benzene rings is 48.16 (5)°. The non-centrosymmetric crystal packing is consistent with the substantial non-zero second harmonic generation response.

Comment

The title compound, (I) (Fig. 1), was prepared as part of our ongoing studies (Harrison et al., 2005 ; Harrison, Yathirajan, Sarojini et al., 2006 ) of the non-linear optical (NLO) properties and crystal structures of chalcone derivatives. It is known that substitution at either benzene ring of the chalcone skeleton substantially affects optical response (Uchida et al., 1998 ) and we are now exploring the role of the methylsulfanyl (H₃CS–) substituent (Harrison, Yathirajan, Mithun et al., 2006 ) in this process.

Compound (I) displays a substantial second harmonic generation (SHG) response to red light of 7.4 times that of urea (Watson et al., 1993 ). This is consistent with its polar space group. The geometrical parameters for (I) fall within their expected ranges (Allen et al., 1987 ). The molecule of (I) is distinctly twisted about the C6—C7 and C9—C10 bonds (Table 1). The dihedral angle between the benzene ring best planes (C1–C6 and C10–C15) in (I) is 48.16 (5)°, which is similiar to the equivalent angle of 45.84 (4)° in 3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (Harrison, Yathirajan, Mithun et al., 2006), but substantially smaller than the 68.15 (6)° seen in 2-bromo-1-(4-methylphenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one (Butcher et al., 2006 ). The C16-methyl group in (I) is slightly displaced from the C10–C15 benzene ring mean plane [deviation = 0.169 (5) Å].

A PLATON (Spek, 2003 ) analysis of (I) indicated a possible intermolecular C—H⋯O interaction (Table 2) that might help to establish the crystal packing, which results in columns of molecules propagating in [001] with all the molecules aligned in the same sense with respect to the polar axis. Then, side-by-side [001] columns of molecules form pseudo-sheets in (010) (Fig. 2). This packing motif is very similar to that seen in 3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (Harrison, Yathirajan, Mithun et al., 2006), although the overall symmetries and unit cells are quite different for these two phases.

Figure 1
View of (I)

showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).

Figure 2
Detail of (I)

showing side-by-side [001] columns forming an (010) pseudo-sheet. The C—H⋯O interactions are shown as dashed lines.

Experimental

Aa aqueous solution of potassium hydroxide (5%, 5 ml) was added slowly with stirring to a mixture of 4-(methylsulfanyl)benzaldehyde (1.52 g, 0.01 mol) and 4-chloroacetophenone (1.54 g, 0.01 mol) in ethanol (15 ml). The resulting mixture was stirred at room temperature for 24 h. The precipitated solid was filtered off, washed with water, dried and plates of (I) were recrystallized from a (1:1 v/v) acetone–toluene mixture (yield 81%; m.p. 415–417 K). Analysis found (calculated) for C₁₆H₁₃ClOS (%): C 66.41 (66.54), H 4.46 (4.54).

Crystal data

C₁₆H₁₃ClOS
M_r = 288.77
Monoclinic, C c
a = 33.371 (2) Å
b = 6.9767 (5) Å
c = 5.8228 (3) Å
β = 90.376 (4)°
V = 1355.63 (14) Å³
Z = 4
D_x = 1.415 Mg m⁻³
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 120 (2) K
Plate, colourless
0.48 × 0.24 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.823, T_max = 0.983
8628 measured reflections
2964 independent reflections
2634 reflections with I > 2σ(I)
R_int = 0.047
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.087
S = 1.05
2964 reflections
173 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0314P)² + 0.6117P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 1399 Friedel pairs
Flack parameter: 0.07 (6)

Table 1
Selected torsion angles (°)

C5—C6—C7—O1	−21.6 (3)
C8—C9—C10—C11	−7.6 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.95	2.59	3.319 (3)	134
Symmetry code: (i) x, y, z+1.

The H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The methyl group was allowed to rotate but not to tip to best fit the electron density.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806037330/lh2180sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806037330/lh2180Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(2E)-1-(4-Chlorophenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one top

Crystal data top

C₁₆H₁₃ClOS	F(000) = 600
M_r = 288.77	D_x = 1.415 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1626 reflections
a = 33.371 (2) Å	θ = 2.9–27.5°
b = 6.9767 (5) Å	µ = 0.42 mm⁻¹
c = 5.8228 (3) Å	T = 120 K
β = 90.376 (4)°	Plate, colourless
V = 1355.63 (14) Å³	0.48 × 0.24 × 0.04 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2964 independent reflections
Radiation source: fine-focus sealed tube	2634 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω and φ scans	θ_max = 27.6°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −43→42
T_min = 0.823, T_max = 0.983	k = −9→9
8628 measured reflections	l = −7→7

Refinement top

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0314P)² + 0.6117P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2964 reflections	Δρ_max = 0.25 e Å⁻³
173 parameters	Δρ_min = −0.27 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1399 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (6)

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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
C1	0.54021 (8)	0.8115 (3)	0.5478 (4)	0.0204 (5)
H1	0.5184	0.8519	0.6400	0.025*
C2	0.57921 (9)	0.8272 (4)	0.6312 (5)	0.0220 (6)
H2	0.5843	0.8802	0.7789	0.026*
C3	0.61055 (8)	0.7644 (4)	0.4957 (4)	0.0216 (5)
C4	0.60414 (8)	0.6857 (4)	0.2795 (4)	0.0221 (6)
H4	0.6259	0.6408	0.1900	0.026*
C5	0.56524 (8)	0.6744 (3)	0.1984 (4)	0.0203 (5)
H5	0.5604	0.6230	0.0498	0.024*
C6	0.53297 (9)	0.7367 (3)	0.3295 (4)	0.0192 (5)
C7	0.49173 (9)	0.7303 (3)	0.2283 (4)	0.0222 (6)
C8	0.45713 (9)	0.7309 (4)	0.3847 (5)	0.0214 (5)
H8	0.4607	0.6982	0.5419	0.026*
C9	0.42085 (8)	0.7773 (4)	0.3059 (4)	0.0194 (6)
H9	0.4195	0.8203	0.1512	0.023*
C10	0.38283 (8)	0.7699 (3)	0.4299 (4)	0.0194 (6)
C11	0.37873 (8)	0.6891 (3)	0.6506 (4)	0.0193 (5)
H11	0.4020	0.6474	0.7315	0.023*
C12	0.34175 (8)	0.6696 (4)	0.7509 (4)	0.0194 (6)
H12	0.3397	0.6145	0.8996	0.023*
C13	0.30687 (8)	0.7306 (3)	0.6350 (4)	0.0190 (5)
C14	0.31051 (8)	0.8129 (3)	0.4189 (4)	0.0207 (5)
H14	0.2873	0.8566	0.3391	0.025*
C15	0.34806 (8)	0.8313 (3)	0.3197 (4)	0.0194 (5)
H15	0.3500	0.8876	0.1717	0.023*
C16	0.22499 (9)	0.7720 (4)	0.5694 (5)	0.0328 (7)
H16A	0.1980	0.7445	0.6258	0.049*
H16B	0.2295	0.7021	0.4259	0.049*
H16C	0.2277	0.9099	0.5417	0.049*
O1	0.48761 (7)	0.7269 (3)	0.0189 (3)	0.0286 (5)
S1	0.26129 (2)	0.69787 (9)	0.77988 (9)	0.02479 (17)
Cl1	0.65933 (2)	0.78324 (11)	0.60236 (9)	0.03329 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0240 (14)	0.0178 (12)	0.0196 (13)	−0.0004 (10)	0.0048 (10)	0.0017 (9)
C2	0.0303 (18)	0.0164 (13)	0.0194 (13)	−0.0007 (12)	0.0000 (11)	−0.0022 (11)
C3	0.0204 (14)	0.0204 (13)	0.0238 (13)	−0.0012 (10)	−0.0038 (10)	0.0040 (10)
C4	0.0218 (14)	0.0189 (13)	0.0256 (13)	0.0013 (10)	0.0036 (11)	−0.0013 (10)
C5	0.0254 (14)	0.0180 (12)	0.0175 (12)	−0.0017 (10)	0.0013 (10)	−0.0006 (9)
C6	0.0229 (14)	0.0130 (11)	0.0217 (13)	−0.0003 (10)	0.0012 (10)	0.0017 (10)
C7	0.0265 (15)	0.0167 (12)	0.0234 (14)	−0.0006 (11)	−0.0012 (11)	−0.0003 (10)
C8	0.0236 (15)	0.0193 (12)	0.0214 (13)	−0.0018 (11)	0.0021 (11)	0.0014 (10)
C9	0.0260 (16)	0.0144 (13)	0.0178 (13)	−0.0018 (10)	−0.0002 (11)	−0.0008 (9)
C10	0.0231 (15)	0.0149 (12)	0.0204 (13)	−0.0002 (10)	−0.0016 (11)	−0.0027 (10)
C11	0.0218 (14)	0.0152 (12)	0.0207 (13)	−0.0002 (10)	−0.0059 (10)	0.0018 (9)
C12	0.0274 (18)	0.0147 (12)	0.0161 (13)	−0.0020 (12)	−0.0024 (11)	−0.0001 (10)
C13	0.0233 (14)	0.0145 (11)	0.0192 (13)	−0.0007 (10)	0.0023 (10)	−0.0036 (9)
C14	0.0225 (14)	0.0196 (13)	0.0201 (12)	0.0021 (11)	−0.0016 (10)	0.0002 (10)
C15	0.0256 (15)	0.0147 (12)	0.0179 (12)	−0.0002 (10)	−0.0015 (10)	0.0000 (9)
C16	0.0185 (15)	0.0423 (16)	0.0375 (16)	0.0030 (13)	−0.0010 (12)	0.0062 (14)
O1	0.0255 (12)	0.0417 (12)	0.0185 (10)	−0.0004 (10)	0.0000 (8)	−0.0006 (8)
S1	0.0227 (4)	0.0266 (4)	0.0251 (3)	−0.0007 (3)	0.0030 (3)	0.0013 (3)
Cl1	0.0237 (4)	0.0407 (4)	0.0354 (4)	−0.0031 (3)	−0.0060 (3)	−0.0009 (3)

Geometric parameters (Å, º) top

C1—C2	1.391 (4)	C9—H9	0.9500
C1—C6	1.394 (3)	C10—C15	1.390 (4)
C1—H1	0.9500	C10—C11	1.411 (3)
C2—C3	1.385 (4)	C11—C12	1.376 (4)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.388 (4)	C12—C13	1.407 (4)
C3—Cl1	1.743 (3)	C12—H12	0.9500
C4—C5	1.381 (4)	C13—C14	1.389 (3)
C4—H4	0.9500	C13—S1	1.759 (3)
C5—C6	1.394 (4)	C14—C15	1.389 (4)
C5—H5	0.9500	C14—H14	0.9500
C6—C7	1.494 (4)	C15—H15	0.9500
C7—O1	1.227 (3)	C16—S1	1.794 (3)
C7—C8	1.475 (4)	C16—H16A	0.9800
C8—C9	1.332 (4)	C16—H16B	0.9800
C8—H8	0.9500	C16—H16C	0.9800
C9—C10	1.465 (4)

C2—C1—C6	120.3 (2)	C10—C9—H9	116.2
C2—C1—H1	119.8	C15—C10—C11	117.2 (2)
C6—C1—H1	119.8	C15—C10—C9	119.0 (2)
C3—C2—C1	119.0 (2)	C11—C10—C9	123.5 (2)
C3—C2—H2	120.5	C12—C11—C10	121.3 (2)
C1—C2—H2	120.5	C12—C11—H11	119.4
C2—C3—C4	121.9 (3)	C10—C11—H11	119.4
C2—C3—Cl1	118.7 (2)	C11—C12—C13	120.5 (2)
C4—C3—Cl1	119.4 (2)	C11—C12—H12	119.7
C5—C4—C3	118.1 (2)	C13—C12—H12	119.7
C5—C4—H4	120.9	C14—C13—C12	118.8 (3)
C3—C4—H4	120.9	C14—C13—S1	124.7 (2)
C4—C5—C6	121.5 (2)	C12—C13—S1	116.47 (19)
C4—C5—H5	119.2	C15—C14—C13	119.9 (2)
C6—C5—H5	119.2	C15—C14—H14	120.0
C5—C6—C1	119.1 (2)	C13—C14—H14	120.0
C5—C6—C7	119.2 (2)	C14—C15—C10	122.2 (2)
C1—C6—C7	121.6 (2)	C14—C15—H15	118.9
O1—C7—C8	122.0 (3)	C10—C15—H15	118.9
O1—C7—C6	119.3 (2)	S1—C16—H16A	109.5
C8—C7—C6	118.6 (2)	S1—C16—H16B	109.5
C9—C8—C7	120.1 (2)	H16A—C16—H16B	109.5
C9—C8—H8	120.0	S1—C16—H16C	109.5
C7—C8—H8	120.0	H16A—C16—H16C	109.5
C8—C9—C10	127.6 (2)	H16B—C16—H16C	109.5
C8—C9—H9	116.2	C13—S1—C16	102.55 (13)

C6—C1—C2—C3	−1.1 (4)	C7—C8—C9—C10	174.3 (2)
C1—C2—C3—C4	−0.2 (4)	C8—C9—C10—C15	177.7 (3)
C1—C2—C3—Cl1	−179.6 (2)	C8—C9—C10—C11	−7.6 (4)
C2—C3—C4—C5	1.3 (4)	C15—C10—C11—C12	0.9 (3)
Cl1—C3—C4—C5	−179.33 (18)	C9—C10—C11—C12	−173.9 (2)
C3—C4—C5—C6	−1.1 (4)	C10—C11—C12—C13	−0.1 (4)
C4—C5—C6—C1	−0.2 (4)	C11—C12—C13—C14	−0.8 (4)
C4—C5—C6—C7	176.9 (2)	C11—C12—C13—S1	179.86 (18)
C2—C1—C6—C5	1.3 (3)	C12—C13—C14—C15	0.9 (3)
C2—C1—C6—C7	−175.7 (2)	S1—C13—C14—C15	−179.79 (19)
C5—C6—C7—O1	−21.6 (3)	C13—C14—C15—C10	−0.1 (4)
C1—C6—C7—O1	155.4 (2)	C11—C10—C15—C14	−0.8 (4)
C5—C6—C7—C8	159.2 (2)	C9—C10—C15—C14	174.3 (2)
C1—C6—C7—C8	−23.8 (3)	C14—C13—S1—C16	5.5 (2)
O1—C7—C8—C9	−17.4 (4)	C12—C13—S1—C16	−175.16 (19)
C6—C7—C8—C9	161.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.59	3.319 (3)	134

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

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection. BKS thanks AICTE, Government of India, New Delhi, for financial assistance under the `Career Award for Young Teachers' scheme.

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