(E)-1-[4-(Methyl­sulfan­yl)phen­yl]-3-phenyl­prop-2-en-1-one

Thiruvalluvar, A.; Subramanyam, M.; Butcher, R.J.; Karabasanagouda, T.; Adhikari, A.V.

doi:10.1107/S1600536808017200

(E)-1-[4-(Methylsulfanyl)phenyl]-3-phenylprop-2-en-1-one

A. Thiruvalluvar, M. Subramanyam, R. J. Butcher, T. Karabasanagouda and A. V. Adhikari

In the title molecule, C₁₆H₁₄OS, the dihedral angle between the phenyl and benzene rings is 3.81 (15)°. The H atoms of the central enone group are trans. The propenone unit makes dihedral angles of 11.73 (18) and 11.62 (17)° with the benzene and phenyl rings, respectively. The crystal structure is stabilized by weak C—H

O and C—H

π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808017200/wn2267sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808017200/wn2267Isup2.hkl Contains datablock I

CCDC reference: 696536

checkCIF report

Key indicators

Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.004 Å
R factor = 0.078
wR factor = 0.182
Data-to-parameter ratio = 24.9

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.966
            Tmax scaled      0.966 Tmin scaled      0.820
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           32.46
           From the CIF: _reflns_number_total               4060
           Count of symmetry unique reflns         2746
           Completeness (_total/calc)            147.85%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1314
           Fraction of Friedel pairs measured     0.479
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound (Fig. 1) has been analysed as part of our crystallographic studies on chalcones (Thiruvalluvar et al. 2007a,b). The dihedral angle between the phenyl and benzene rings is 3.81 (15)°; the two rings are essentially coplanar. The H atoms of the central enone group are trans. The propenone unit makes dihedral angles of 11.73 (18)° and 11.62 (17)° with the benzene and phenyl rings, respectively.

The crystal structure is stabilized by a weak C3—H3···O1 intramolecular interaction. Furthermore, C12—H12···π, C15—H15···π and C25—H25···π interactions are also found. In similar structures, such as 1-(4-aminophenyl)-3-(3-bromophenyl)-prop-2-en-1-one (Sathiya Moorthi, et al. 2005) and 1-(4-bromophenyl)-3-(3-hydroxy phenyl)prop-2-en-1-one (Moorthi, et al. 2005), the dihedral angles between the two rings are 9.6 (1)° and 10.2 (2)°, respectively.

Related literature top

For related crystal structures, see Sathiya Moorthi, et al. (2005); Moorthi, et al. (2005); Thiruvalluvar, et al. (2007a,b). Cg1 and Cg2 are the centroids of the C11–C16 and C21–C26 rings, respectively.

Experimental top

Benzaldehyde (2.12 g, 0.02 mol) in ethanol (22 ml) was mixed with 4'-(methylthio)acetophenone (3.32 g, 0.02 mol) in 40 ml ethanol and the mixture was treated with 10 ml of 10% sodium hydroxide solution at 283 K and stirred at 303–305 K for 8 h. The precipitate obtained was filtered, washed with chilled ethanol and dried. Pale yellow rods of the title compound were grown from toluene by slow evaporation. The yield of the isolated product was 3.4 g (70%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are represented by spheres of arbitrary radius.

(E)-1-[4-(Methylsulfanyl)phenyl]-3-phenylprop-2-en-1-one top

Crystal data top

C₁₆H₁₄OS	D_x = 1.296 Mg m⁻³
M_r = 254.34	Melting point: 396(1) K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3999 reflections
a = 5.6106 (4) Å	θ = 4.7–32.4°
b = 7.6239 (7) Å	µ = 0.23 mm⁻¹
c = 30.477 (2) Å	T = 200 K
V = 1303.64 (17) Å³	Needle, colourless
Z = 4	0.49 × 0.18 × 0.15 mm
F(000) = 536

Data collection top

Oxford Diffraction Gemini diffractometer	4060 independent reflections
Radiation source: fine-focus sealed tube	3180 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.5°, θ_min = 4.7°
ϕ and ω scans	h = −6→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −11→10
T_min = 0.849, T_max = 1.000	l = −45→38
8924 measured reflections

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)] = 0.077	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + (0.0605P)² + 1.4543P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
4060 reflections	Δρ_max = 0.69 e Å⁻³
163 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1314 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (16)

Crystal data top

C₁₆H₁₄OS	V = 1303.64 (17) Å³
M_r = 254.34	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.6106 (4) Å	µ = 0.23 mm⁻¹
b = 7.6239 (7) Å	T = 200 K
c = 30.477 (2) Å	0.49 × 0.18 × 0.15 mm

Data collection top

Oxford Diffraction Gemini diffractometer	4060 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	3180 reflections with I > 2σ(I)
T_min = 0.849, T_max = 1.000	R_int = 0.069
8924 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	H-atom parameters constrained
wR(F²) = 0.182	Δρ_max = 0.69 e Å⁻³
S = 1.11	Δρ_min = −0.38 e Å⁻³
4060 reflections	Absolute structure: Flack (1983), 1314 Friedel pairs
163 parameters	Absolute structure parameter: 0.11 (16)
0 restraints

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
S4	0.48075 (18)	0.98501 (13)	−0.09063 (3)	0.0418 (3)
O1	0.8645 (4)	1.0222 (4)	0.11787 (7)	0.0411 (8)
C1	0.6679 (5)	0.9800 (4)	0.10480 (9)	0.0284 (8)
C2	0.4803 (6)	0.9187 (4)	0.13565 (9)	0.0300 (8)
C3	0.5318 (6)	0.8989 (4)	0.17807 (9)	0.0273 (8)
C4	0.7257 (8)	1.0997 (6)	−0.11513 (11)	0.0481 (13)
C11	0.3725 (6)	0.8391 (4)	0.21292 (9)	0.0269 (8)
C12	0.4425 (5)	0.8603 (4)	0.25687 (9)	0.0284 (8)
C13	0.2984 (7)	0.8019 (5)	0.29078 (10)	0.0349 (10)
C14	0.0835 (7)	0.7219 (5)	0.28169 (11)	0.0374 (10)
C15	0.0098 (7)	0.6998 (4)	0.23848 (10)	0.0335 (9)
C16	0.1525 (6)	0.7588 (4)	0.20435 (10)	0.0306 (9)
C21	0.6093 (5)	0.9893 (4)	0.05707 (9)	0.0239 (7)
C22	0.7753 (5)	1.0701 (4)	0.02917 (10)	0.0285 (8)
C23	0.7412 (6)	1.0748 (4)	−0.01573 (10)	0.0296 (8)
C24	0.5389 (6)	0.9955 (4)	−0.03416 (9)	0.0281 (8)
C25	0.3704 (5)	0.9185 (4)	−0.00654 (10)	0.0293 (8)
C26	0.4044 (6)	0.9151 (4)	0.03850 (10)	0.0300 (8)
H2	0.32442	0.89374	0.12518	0.0360*
H3	0.69018	0.92687	0.18661	0.0328*
H4A	0.70702	1.09997	−0.14710	0.0720*
H4B	0.87527	1.04105	−0.10734	0.0720*
H4C	0.72878	1.22076	−0.10434	0.0720*
H12	0.59023	0.91523	0.26341	0.0340*
H13	0.34767	0.81704	0.32036	0.0419*
H14	−0.01452	0.68175	0.30504	0.0449*
H15	−0.13808	0.64431	0.23233	0.0402*
H16	0.10064	0.74459	0.17489	0.0367*
H22	0.91377	1.12262	0.04138	0.0341*
H23	0.85442	1.13149	−0.03407	0.0356*
H25	0.23077	0.86768	−0.01875	0.0351*
H26	0.28802	0.86225	0.05687	0.0360*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S4	0.0460 (5)	0.0497 (5)	0.0297 (3)	−0.0035 (5)	−0.0048 (3)	−0.0008 (3)
O1	0.0278 (12)	0.0601 (17)	0.0353 (11)	−0.0141 (13)	−0.0040 (9)	0.0017 (11)
C1	0.0259 (14)	0.0295 (15)	0.0297 (12)	−0.0040 (13)	0.0011 (10)	−0.0007 (11)
C2	0.0243 (14)	0.0349 (15)	0.0308 (12)	−0.0088 (13)	0.0007 (11)	0.0004 (11)
C3	0.0215 (14)	0.0254 (13)	0.0350 (13)	−0.0010 (12)	0.0022 (11)	−0.0006 (11)
C4	0.051 (2)	0.059 (3)	0.0342 (16)	−0.005 (2)	0.0029 (15)	0.0084 (17)
C11	0.0248 (14)	0.0252 (14)	0.0307 (13)	0.0026 (12)	0.0026 (11)	0.0010 (11)
C12	0.0218 (15)	0.0295 (15)	0.0338 (14)	0.0040 (11)	−0.0026 (11)	−0.0009 (11)
C13	0.0377 (18)	0.0378 (18)	0.0293 (14)	0.0044 (15)	0.0003 (13)	0.0019 (12)
C14	0.0379 (19)	0.0348 (18)	0.0396 (17)	0.0129 (14)	0.0114 (13)	0.0081 (14)
C15	0.0303 (16)	0.0246 (14)	0.0456 (16)	−0.0027 (14)	0.0050 (14)	0.0008 (11)
C16	0.0262 (15)	0.0323 (16)	0.0332 (14)	0.0015 (13)	−0.0002 (12)	−0.0002 (12)
C21	0.0210 (12)	0.0210 (12)	0.0297 (12)	0.0003 (11)	0.0004 (9)	0.0002 (11)
C22	0.0213 (13)	0.0300 (15)	0.0341 (14)	−0.0069 (12)	0.0002 (11)	0.0004 (12)
C23	0.0255 (14)	0.0295 (15)	0.0339 (14)	−0.0023 (12)	0.0034 (11)	0.0025 (12)
C24	0.0326 (15)	0.0220 (12)	0.0297 (12)	0.0040 (13)	−0.0023 (10)	0.0004 (11)
C25	0.0202 (13)	0.0319 (15)	0.0357 (14)	−0.0070 (12)	−0.0032 (11)	−0.0034 (12)
C26	0.0258 (15)	0.0316 (15)	0.0327 (14)	−0.0035 (13)	0.0022 (11)	0.0001 (12)

Geometric parameters (Å, º) top

S4—C4	1.792 (4)	C24—C25	1.395 (4)
S4—C24	1.754 (3)	C25—C26	1.386 (4)
O1—C1	1.216 (4)	C2—H2	0.9500
C1—C2	1.487 (4)	C3—H3	0.9500
C1—C21	1.493 (4)	C4—H4A	0.9800
C2—C3	1.333 (4)	C4—H4B	0.9800
C3—C11	1.461 (4)	C4—H4C	0.9800
C11—C12	1.405 (4)	C12—H12	0.9500
C11—C16	1.402 (5)	C13—H13	0.9500
C12—C13	1.386 (4)	C14—H14	0.9500
C13—C14	1.379 (5)	C15—H15	0.9500
C14—C15	1.391 (5)	C16—H16	0.9500
C15—C16	1.388 (5)	C22—H22	0.9500
C21—C22	1.404 (4)	C23—H23	0.9500
C21—C26	1.401 (4)	C25—H25	0.9500
C22—C23	1.382 (4)	C26—H26	0.9500
C23—C24	1.403 (5)

S4···H16ⁱ	3.1800	H2···C26	2.6800
O1···H2ⁱⁱ	2.7700	H2···H16	2.2700
O1···H3	2.4200	H2···H26	2.1100
O1···H22	2.4700	H3···O1	2.4200
O1···H4Cⁱⁱⁱ	2.8600	H3···C15ⁱⁱ	2.9500
O1···H14^iv	2.7800	H3···C16ⁱⁱ	2.9400
C3···C13^iv	3.354 (5)	H3···H12	2.4100
C3···C14^iv	3.497 (5)	H3···C13^iv	2.9400
C3···C15ⁱⁱ	3.590 (5)	H3···C14^iv	2.7600
C12···C15ⁱⁱ	3.456 (5)	H4A···C14^x	3.0300
C13···C3^v	3.354 (5)	H4A···H14^x	2.4600
C14···C3^v	3.497 (5)	H4B···C23	2.9000
C15···C12^vi	3.456 (5)	H4B···H23	2.3400
C15···C3^vi	3.590 (5)	H4C···C23	2.9200
C2···H16	2.7800	H4C···H23	2.3600
C2···H26	2.6700	H4C···O1^ix	2.8600
C4···H23	2.5900	H12···C15ⁱⁱ	2.9700
C12···H15^vii	2.7800	H12···H3	2.4100
C12···H15ⁱⁱ	2.9700	H14···H4A^viii	2.4600
C13···H15^vii	2.8500	H14···O1^v	2.7800
C13···H3^v	2.9400	H15···C12^vi	2.9700
C14···H3^v	2.7600	H15···C12^xi	2.7800
C14···H4A^viii	3.0300	H15···C13^xi	2.8500
C15···H3^vi	2.9500	H16···C2	2.7800
C15···H12^vi	2.9700	H16···H2	2.2700
C16···H2	2.7900	H16···S4^xii	3.1800
C16···H3^vi	2.9400	H22···O1	2.4700
C21···H25ⁱ	3.0400	H22···C23ⁱⁱⁱ	3.0500
C23···H4B	2.9000	H22···C24ⁱⁱⁱ	3.0000
C23···H4C	2.9200	H23···C4	2.5900
C23···H22^ix	3.0500	H23···H4B	2.3400
C24···H22^ix	3.0000	H23···H4C	2.3600
C25···H25ⁱ	3.0700	H25···C21^xii	3.0400
C26···H2	2.6800	H25···C25^xii	3.0700
C26···H25ⁱ	2.8900	H25···C26^xii	2.8900
H2···O1^vi	2.7700	H26···C2	2.6700
H2···C16	2.7900	H26···H2	2.1100

C4—S4—C24	104.13 (16)	C2—C3—H3	116.00
O1—C1—C2	121.2 (3)	C11—C3—H3	116.00
O1—C1—C21	120.4 (3)	S4—C4—H4A	109.00
C2—C1—C21	118.4 (2)	S4—C4—H4B	109.00
C1—C2—C3	119.7 (3)	S4—C4—H4C	109.00
C2—C3—C11	127.4 (3)	H4A—C4—H4B	109.00
C3—C11—C12	119.1 (3)	H4A—C4—H4C	109.00
C3—C11—C16	122.6 (3)	H4B—C4—H4C	109.00
C12—C11—C16	118.3 (3)	C11—C12—H12	120.00
C11—C12—C13	120.7 (3)	C13—C12—H12	120.00
C12—C13—C14	120.2 (3)	C12—C13—H13	120.00
C13—C14—C15	120.3 (3)	C14—C13—H13	120.00
C14—C15—C16	119.9 (3)	C13—C14—H14	120.00
C11—C16—C15	120.7 (3)	C15—C14—H14	120.00
C1—C21—C22	117.7 (3)	C14—C15—H15	120.00
C1—C21—C26	123.7 (3)	C16—C15—H15	120.00
C22—C21—C26	118.5 (3)	C11—C16—H16	120.00
C21—C22—C23	121.3 (3)	C15—C16—H16	120.00
C22—C23—C24	119.8 (3)	C21—C22—H22	119.00
S4—C24—C23	124.3 (2)	C23—C22—H22	119.00
S4—C24—C25	116.5 (2)	C22—C23—H23	120.00
C23—C24—C25	119.2 (3)	C24—C23—H23	120.00
C24—C25—C26	120.8 (3)	C24—C25—H25	120.00
C21—C26—C25	120.4 (3)	C26—C25—H25	120.00
C1—C2—H2	120.00	C21—C26—H26	120.00
C3—C2—H2	120.00	C25—C26—H26	120.00

C4—S4—C24—C23	−1.6 (3)	C11—C12—C13—C14	0.0 (5)
C4—S4—C24—C25	178.6 (3)	C12—C13—C14—C15	−0.2 (6)
O1—C1—C2—C3	−4.2 (5)	C13—C14—C15—C16	−0.2 (5)
C21—C1—C2—C3	176.0 (3)	C14—C15—C16—C11	0.7 (5)
O1—C1—C21—C22	−8.6 (4)	C1—C21—C22—C23	176.1 (3)
O1—C1—C21—C26	168.4 (3)	C26—C21—C22—C23	−1.0 (5)
C2—C1—C21—C22	171.3 (3)	C1—C21—C26—C25	−175.5 (3)
C2—C1—C21—C26	−11.8 (4)	C22—C21—C26—C25	1.4 (5)
C1—C2—C3—C11	−179.5 (3)	C21—C22—C23—C24	−0.9 (5)
C2—C3—C11—C12	−167.1 (3)	C22—C23—C24—S4	−177.5 (2)
C2—C3—C11—C16	13.8 (5)	C22—C23—C24—C25	2.4 (5)
C3—C11—C12—C13	−178.7 (3)	S4—C24—C25—C26	177.9 (2)
C16—C11—C12—C13	0.5 (5)	C23—C24—C25—C26	−1.9 (5)
C3—C11—C16—C15	178.3 (3)	C24—C25—C26—C21	0.0 (5)
C12—C11—C16—C15	−0.9 (5)

Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) x+1, y, z; (iii) x+1/2, −y+5/2, −z; (iv) −x+1, y+1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) x−1, y, z; (vii) −x, y+1/2, −z+1/2; (viii) −x+1/2, −y+2, z+1/2; (ix) x−1/2, −y+5/2, −z; (x) −x+1/2, −y+2, z−1/2; (xi) −x, y−1/2, −z+1/2; (xii) x−1/2, −y+3/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1	0.95	2.42	2.781 (4)	102
C12—H12···Cg1^iv	0.95	2.99	3.704 (3)	133
C15—H15···Cg1^xi	0.95	2.89	3.488 (3)	122
C25—H25···Cg2^xii	0.95	2.90	3.562 (3)	127

Symmetry codes: (iv) −x+1, y+1/2, −z+1/2; (xi) −x, y−1/2, −z+1/2; (xii) x−1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄OS
M_r	254.34
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	200
a, b, c (Å)	5.6106 (4), 7.6239 (7), 30.477 (2)
V (Å³)	1303.64 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.49 × 0.18 × 0.15

Data collection
Diffractometer	Oxford Diffraction Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.849, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8924, 4060, 3180
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.755

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.182, 1.11
No. of reflections	4060
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.38
Absolute structure	Flack (1983), 1314 Friedel pairs
Absolute structure parameter	0.11 (16)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).