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Acta Cryst. (2007). E63, o3731-o3732    [ doi:10.1107/S1600536807038147 ]

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

R. J. Butcher, J. P. Jasinski, H. S. Yathirajan, B. Narayana and A. Mithun

Abstract top

In the title molecule, C16H13BrOS, the mean planes of the 4-bromophenyl and 4-(methylsulfanyl)phenyl groups are twisted by 47.4 (2)° from each other. The angles between the mean plane of the prop-2-en-1-one group and those of the 4-bromophenyl and 4-(methylsulfanyl)phenyl groups are 21.1 (4) and 26.3 (2)°, respectively. Crystal packing is characterized by alignment of adjacent molecules syn to each other, oblique to the ac plane and stacked in parallel arrays along the c axis of the unit cell. The closest distance between 4-bromophenyl rings is 4.536 (2) Å; that between 4-(methylsulfanyl)phenyl groups is 4.539 (2) Å.

Comment top

Chalcones possess a broad spectrum of biological activities, including antibacterial, antihelmintic, amoebicidal, anti-ulcer, antiviral, insecticidal, antiprotozoal, anticancer, cytotoxic and immunosuppressive activities. Among the various organic compounds reported for their non-linear optical (NLO) properties, chalcone derivatives are notable for their excellent blue-light transmittance and good crystallizability. They provide a necessary molecular electronic configuration to show NLO effects, with two aromatic rings connected through a conjugated bridge. Substitution on either of the benzene rings appears to increase the likelihood of non-centrosymmetric crystal packing, as well as enhancing the electronic properties of the molecule. The molecular hyperpolarizability β are strongly influenced not only by the electronic effect but also by the steric effect of the substituent. In continuation of our quest to discover newer materials, we have synthesized a new chalcone derivative and studied its SHG efficiency. The SHG efficiency of the title compound is found to be five times that of urea. In view of the importance of the title compound, (I), C16H13BrOS, a crystal structure is reported here.

The mean planes of the 4-bromophenyl and 4-(methylsulfanyl)phenyl groups are coplanar and twisted by 47.4 (2)° from each other (Fig. 1). The angles between the mean plane of the prop-2-en-1-one group and that of the 4-bromophenyl [torsion angle (C8–C7–C1–C2) = 159.15 (18) °] and 4-(methylsulfanyl)phenyl [torsion angle (C8–C9–C10–C15) = 178.5 (2)°] groups are 21.1 (4)° and 26.3 (2)°, respectively.

Crystal packing is highlighted by alignment of adjacent molecules syn to each other, oblique to the ac plane and stacked in parallel arrays along the c axis of the unit cell. The closest distance between mean planes of the coplanar 4-bromophenyl and 4-(methylsulfanyl)phenyl groups is 4.536 (2) and 4.539 (2) Å, respectively (Fig. 2).

Related literature top

For related structures, see: Butcher, Yathirajan, Sarojini et al. (2006); Butcher, Yathirajan, Anilkumar et al. 2006a,b,c). For related background, see: Dimmock et al. (1999); Lawrence et al. (2001); Phrutivorapongkul et al. (2003); Xia et al. (2000); Pandey et al. (2005); Uchida et al. (1998); Goto et al. (1991); Tam et al. (1989); Indira et al. (2002); Fichou et al. (1988) and Cho et al. (1996).

Experimental top

To a mixture of 4-methylsulfanylbenzaldehyde (1.52 g, 0.01 mol) and 4-bromo-acetophenone (1.99 g, 0.01 mol) in ethanol (25 ml), a solution of potassium hydroxide (5%, 5 ml) was added slowly with stirring (Fig. 3). The mixture was stirred at room temperature for 24 h. The precipitated solid was filtered, washed with water, dried and recrystallized from acetone- toluene mixture (9:1), with a yield of 85% (m.p.: 430 K). Analysis found: C 57.55, H 3.72%; C16H13BrOS requires: C 57.67, H 3.93%.

Refinement top

The H atoms were included in the riding model approximation with C—H = 0.95–0.98 Å, and with Uiso(H) = 1.17–1.50Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. Molecular structure for C16H13BrOS, (I), showing atom labeling and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram of C16H13ClBrOS viewed down the b axis.
[Figure 3] Fig. 3. The formation of the title compound, C16H13BrOS.
(2E)-1-(4-Bromophenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one top
Crystal data top
C16H13BrOSF000 = 672
Mr = 333.23Dx = 1.614 Mg m−3
Monoclinic, CcMo Kα radiation
λ = 0.71073 Å
a = 33.729 (6) ÅCell parameters from 7711 reflections
b = 6.9503 (12) Åθ = 2.4–30.7º
c = 5.8487 (10) ŵ = 3.14 mm−1
β = 90.868 (3)ºT = 100 K
V = 1371.0 (4) Å3Block, colourless
Z = 40.60 × 0.50 × 0.39 mm
Data collection top
Bruker APEXII CCD
diffractometer		2086 independent reflections
Radiation source: fine-focus sealed tube1986 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
T = 100 Kθmax = 30.6º
ω scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −48→47
Tmin = 0.515, Tmax = 1.000k = −9→9
7498 measured reflectionsl = −8→8
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035  w = 1/[σ2(Fo2)]
wR(F2) = 0.078(Δ/σ)max = 0.001
S = 1.53Δρmax = 1.05 e Å−3
2086 reflectionsΔρmin = −0.45 e Å−3
173 parametersExtinction correction: none
2 restraintsAbsolute structure: Flack (1983), with 1949 anomalous pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.016 (5)
Secondary atom site location: difference Fourier map
Crystal data top
C16H13BrOSV = 1371.0 (4) Å3
Mr = 333.23Z = 4
Monoclinic, CcMo Kα
a = 33.729 (6) ŵ = 3.14 mm−1
b = 6.9503 (12) ÅT = 100 K
c = 5.8487 (10) Å0.60 × 0.50 × 0.39 mm
β = 90.868 (3)º
Data collection top
Bruker APEXII CCD
diffractometer		2086 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1986 reflections with I > 2σ(I)
Tmin = 0.515, Tmax = 1.000Rint = 0.049
7498 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.078Δρmax = 1.05 e Å−3
S = 1.53Δρmin = −0.45 e Å−3
2086 reflectionsAbsolute structure: Flack (1983), with 1949 anomalous pairs
173 parametersFlack parameter: 0.016 (5)
2 restraints
Special details top

Experimental. 1H NMR (CD2Cl2) δ 7.88 (d, 2H), 7.77 (d, 1H), 7.64 (d, 2H), 7.55 (d, 1H), 7.42 (d, 1H), 7.26 (d, 2H), 2.52 (s, 3H).

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 > 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
xyzUiso*/Ueq
Br1.120444 (16)0.21264 (5)0.47652 (4)0.02440 (11)
S0.72237 (3)0.30093 (13)0.31258 (15)0.0207 (2)
O0.94871 (10)0.2763 (4)1.0726 (5)0.0253 (6)
C10.99256 (13)0.2650 (5)0.7622 (7)0.0181 (7)
C21.02506 (12)0.3265 (5)0.8931 (7)0.0182 (7)
H2A1.02090.37821.04110.022*
C31.06277 (13)0.3137 (5)0.8122 (7)0.0193 (7)
H3A1.08470.35870.90110.023*
C41.06860 (13)0.2320 (5)0.5932 (7)0.0197 (7)
C51.03697 (12)0.1710 (5)0.4606 (7)0.0187 (7)
H5A1.04120.11720.31360.022*
C60.99861 (12)0.1887 (5)0.5438 (7)0.0182 (7)
H6A0.97660.14910.45230.022*
C70.95225 (14)0.2734 (5)0.8619 (7)0.0200 (7)
C80.91725 (15)0.2746 (5)0.7062 (7)0.0188 (7)
H8A0.91990.31090.55060.023*
C90.88213 (15)0.2243 (5)0.7859 (7)0.0177 (7)
H9A0.88170.17830.93880.021*
C100.84376 (14)0.2322 (5)0.6626 (7)0.0160 (7)
C110.83901 (11)0.3127 (5)0.4409 (6)0.0169 (7)
H11A0.86170.35440.36050.020*
C120.80217 (12)0.3315 (5)0.3408 (6)0.0171 (7)
H12A0.79960.38700.19280.020*
C130.76798 (12)0.2691 (5)0.4555 (6)0.0166 (7)
C140.77203 (12)0.1864 (5)0.6720 (7)0.0173 (7)
H14A0.74940.14190.75060.021*
C150.80961 (12)0.1698 (5)0.7717 (6)0.0158 (7)
H15A0.81210.11390.91950.019*
C160.68734 (13)0.2242 (6)0.5225 (8)0.0285 (9)
H16A0.66030.24450.46330.043*
H16B0.69130.29900.66300.043*
H16C0.69130.08730.55550.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br0.01786 (18)0.03035 (19)0.02513 (18)0.0017 (2)0.00495 (13)−0.0012 (2)
S0.0181 (5)0.0240 (5)0.0198 (4)0.0002 (3)−0.0026 (4)0.0017 (4)
O0.0216 (16)0.0394 (18)0.0150 (13)0.0021 (13)−0.0020 (12)0.0013 (12)
C10.0207 (19)0.0169 (16)0.0167 (16)0.0017 (13)0.0015 (14)0.0028 (13)
C20.0232 (19)0.0111 (14)0.0203 (16)0.0024 (12)−0.0008 (14)−0.0009 (13)
C30.0199 (17)0.0184 (17)0.0194 (18)−0.0007 (13)−0.0033 (14)0.0002 (13)
C40.0225 (19)0.0168 (16)0.0200 (17)0.0019 (13)0.0023 (14)0.0025 (13)
C50.023 (2)0.0164 (16)0.0172 (17)0.0024 (13)0.0023 (15)0.0000 (13)
C60.0201 (18)0.0152 (16)0.0193 (16)0.0007 (12)−0.0037 (14)0.0010 (13)
C70.022 (2)0.0162 (16)0.0213 (18)0.0031 (14)−0.0021 (16)−0.0008 (14)
C80.019 (2)0.0206 (19)0.0172 (17)−0.0005 (14)−0.0021 (16)−0.0015 (14)
C90.023 (2)0.0154 (17)0.0144 (16)−0.0014 (14)0.0000 (15)−0.0011 (13)
C100.019 (2)0.0135 (16)0.0152 (17)−0.0028 (13)0.0016 (16)0.0000 (13)
C110.0184 (17)0.0162 (16)0.0161 (16)−0.0003 (11)0.0032 (14)0.0000 (12)
C120.0224 (19)0.0142 (14)0.0147 (17)−0.0013 (14)0.0020 (14)0.0001 (13)
C130.0182 (18)0.0173 (16)0.0143 (15)−0.0001 (12)−0.0001 (14)−0.0003 (12)
C140.0177 (19)0.0172 (16)0.0170 (16)−0.0024 (13)0.0036 (14)−0.0019 (13)
C150.0177 (19)0.0157 (15)0.0139 (16)0.0004 (13)0.0007 (14)−0.0013 (13)
C160.016 (2)0.040 (2)0.029 (2)−0.0035 (16)0.0028 (17)0.0044 (18)
Geometric parameters (Å, °) top
Br—C41.892 (4)C8—H8A0.9500
S—C131.754 (4)C9—C101.473 (7)
S—C161.798 (5)C9—H9A0.9500
O—C71.240 (5)C10—C151.395 (6)
C1—C21.394 (6)C10—C111.419 (5)
C1—C61.401 (5)C11—C121.372 (6)
C1—C71.489 (6)C11—H11A0.9500
C2—C31.367 (6)C12—C131.411 (5)
C2—H2A0.9500C12—H12A0.9500
C3—C41.417 (5)C13—C141.395 (5)
C3—H3A0.9500C14—C151.392 (6)
C4—C51.377 (6)C14—H14A0.9500
C5—C61.394 (6)C15—H15A0.9500
C5—H5A0.9500C16—H16A0.9800
C6—H6A0.9500C16—H16B0.9800
C7—C81.480 (6)C16—H16C0.9800
C8—C91.326 (6)
C13—S—C16102.6 (2)C8—C9—H9A116.5
C2—C1—C6119.5 (4)C10—C9—H9A116.5
C2—C1—C7119.2 (3)C15—C10—C11117.3 (4)
C6—C1—C7121.2 (4)C15—C10—C9119.3 (3)
C3—C2—C1121.2 (3)C11—C10—C9123.2 (4)
C3—C2—H2A119.4C12—C11—C10121.1 (4)
C1—C2—H2A119.4C12—C11—H11A119.4
C2—C3—C4118.8 (4)C10—C11—H11A119.4
C2—C3—H3A120.6C11—C12—C13120.6 (4)
C4—C3—H3A120.6C11—C12—H12A119.7
C5—C4—C3121.0 (4)C13—C12—H12A119.7
C5—C4—Br119.2 (3)C14—C13—C12119.3 (4)
C3—C4—Br119.7 (3)C14—C13—S123.9 (3)
C4—C5—C6119.4 (4)C12—C13—S116.9 (3)
C4—C5—H5A120.3C15—C14—C13119.4 (4)
C6—C5—H5A120.3C15—C14—H14A120.3
C5—C6—C1120.0 (4)C13—C14—H14A120.3
C5—C6—H6A120.0C14—C15—C10122.4 (4)
C1—C6—H6A120.0C14—C15—H15A118.8
O—C7—C8121.6 (4)C10—C15—H15A118.8
O—C7—C1119.5 (4)S—C16—H16A109.5
C8—C7—C1118.9 (4)S—C16—H16B109.5
C9—C8—C7119.4 (4)H16A—C16—H16B109.5
C9—C8—H8A120.3S—C16—H16C109.5
C7—C8—H8A120.3H16A—C16—H16C109.5
C8—C9—C10126.9 (4)H16B—C16—H16C109.5
C6—C1—C2—C30.0 (5)C7—C8—C9—C10174.5 (3)
C7—C1—C2—C3177.2 (3)C8—C9—C10—C15178.7 (4)
C1—C2—C3—C4−1.5 (5)C8—C9—C10—C11−5.6 (6)
C2—C3—C4—C51.7 (5)C15—C10—C11—C121.2 (5)
C2—C3—C4—Br179.9 (3)C9—C10—C11—C12−174.5 (3)
C3—C4—C5—C6−0.4 (5)C10—C11—C12—C13−0.6 (5)
Br—C4—C5—C6−178.6 (3)C11—C12—C13—C14−0.5 (5)
C4—C5—C6—C1−1.1 (5)C11—C12—C13—S179.7 (3)
C2—C1—C6—C51.4 (5)C16—S—C13—C144.9 (4)
C7—C1—C6—C5−175.8 (3)C16—S—C13—C12−175.2 (3)
C2—C1—C7—O−22.1 (5)C12—C13—C14—C150.9 (5)
C6—C1—C7—O155.0 (4)S—C13—C14—C15−179.2 (3)
C2—C1—C7—C8159.0 (3)C13—C14—C15—C10−0.3 (5)
C6—C1—C7—C8−23.9 (5)C11—C10—C15—C14−0.8 (5)
O—C7—C8—C9−19.0 (6)C9—C10—C15—C14175.1 (3)
C1—C7—C8—C9159.8 (3)
Acknowledgements top

AM thanks Mangalore University for the use of their research facilities. RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory for access to their diffractometers.

references
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