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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.035
• wR factor = 0.078
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.29
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.31
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

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      0.294
            Tmax scaled      0.294 Tmin scaled      0.151
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           30.63
           From the CIF: _reflns_number_total               2086
           Count of symmetry unique reflns         2112
           Completeness (_total/calc)             98.77%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_2_G Flack Parameter Value Deviates 2 * su from zero.       0.02
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

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

Computing details

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

	Fig. 1. Molecular structure for C16H13BrOS, (I), showing atom labeling and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of C16H13ClBrOS viewed down the b axis.
	Fig. 3. The formation of the title compound, C16H13BrOS.

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

Crystal data

C16H13BrOS	F(000) = 672
Mr = 333.23	Dx = 1.614 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 33.729 (6) Å	Cell parameters from 7711 reflections
b = 6.9503 (12) Å	θ = 2.4–30.7°
c = 5.8487 (10) Å	µ = 3.14 mm^−1
β = 90.868 (3)°	T = 100 K
V = 1371.0 (4) Å^3	Block, colourless
Z = 4	0.60 × 0.50 × 0.39 mm

Data collection

Bruker APEXII CCD diffractometer	2086 independent reflections
Radiation source: fine-focus sealed tube	1986 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 30.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −48→47
Tmin = 0.515, Tmax = 1.000	k = −9→9
7498 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2)]
S = 1.53	(Δ/σ)max = 0.001
2086 reflections	Δρmax = 1.05 e Å^−3
173 parameters	Δρmin = −0.45 e Å^−3
2 restraints	Absolute structure: Flack (1983), with 1949 anomalous pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.016 (5)

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
Br	1.120444 (16)	0.21264 (5)	0.47652 (4)	0.02440 (11)
S	0.72237 (3)	0.30093 (13)	0.31258 (15)	0.0207 (2)
O	0.94871 (10)	0.2763 (4)	1.0726 (5)	0.0253 (6)
C1	0.99256 (13)	0.2650 (5)	0.7622 (7)	0.0181 (7)
C2	1.02506 (12)	0.3265 (5)	0.8931 (7)	0.0182 (7)
H2A	1.0209	0.3782	1.0411	0.022*
C3	1.06277 (13)	0.3137 (5)	0.8122 (7)	0.0193 (7)
H3A	1.0847	0.3587	0.9011	0.023*
C4	1.06860 (13)	0.2320 (5)	0.5932 (7)	0.0197 (7)
C5	1.03697 (12)	0.1710 (5)	0.4606 (7)	0.0187 (7)
H5A	1.0412	0.1172	0.3136	0.022*
C6	0.99861 (12)	0.1887 (5)	0.5438 (7)	0.0182 (7)
H6A	0.9766	0.1491	0.4523	0.022*
C7	0.95225 (14)	0.2734 (5)	0.8619 (7)	0.0200 (7)
C8	0.91725 (15)	0.2746 (5)	0.7062 (7)	0.0188 (7)
H8A	0.9199	0.3109	0.5506	0.023*
C9	0.88213 (15)	0.2243 (5)	0.7859 (7)	0.0177 (7)
H9A	0.8817	0.1783	0.9388	0.021*
C10	0.84376 (14)	0.2322 (5)	0.6626 (7)	0.0160 (7)
C11	0.83901 (11)	0.3127 (5)	0.4409 (6)	0.0169 (7)
H11A	0.8617	0.3544	0.3605	0.020*
C12	0.80217 (12)	0.3315 (5)	0.3408 (6)	0.0171 (7)
H12A	0.7996	0.3870	0.1928	0.020*
C13	0.76798 (12)	0.2691 (5)	0.4555 (6)	0.0166 (7)
C14	0.77203 (12)	0.1864 (5)	0.6720 (7)	0.0173 (7)
H14A	0.7494	0.1419	0.7506	0.021*
C15	0.80961 (12)	0.1698 (5)	0.7717 (6)	0.0158 (7)
H15A	0.8121	0.1139	0.9195	0.019*
C16	0.68734 (13)	0.2242 (6)	0.5225 (8)	0.0285 (9)
H16A	0.6603	0.2445	0.4633	0.043*
H16B	0.6913	0.2990	0.6630	0.043*
H16C	0.6913	0.0873	0.5555	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br	0.01786 (18)	0.03035 (19)	0.02513 (18)	0.0017 (2)	0.00495 (13)	−0.0012 (2)
S	0.0181 (5)	0.0240 (5)	0.0198 (4)	0.0002 (3)	−0.0026 (4)	0.0017 (4)
O	0.0216 (16)	0.0394 (18)	0.0150 (13)	0.0021 (13)	−0.0020 (12)	0.0013 (12)
C1	0.0207 (19)	0.0169 (16)	0.0167 (16)	0.0017 (13)	0.0015 (14)	0.0028 (13)
C2	0.0232 (19)	0.0111 (14)	0.0203 (16)	0.0024 (12)	−0.0008 (14)	−0.0009 (13)
C3	0.0199 (17)	0.0184 (17)	0.0194 (18)	−0.0007 (13)	−0.0033 (14)	0.0002 (13)
C4	0.0225 (19)	0.0168 (16)	0.0200 (17)	0.0019 (13)	0.0023 (14)	0.0025 (13)
C5	0.023 (2)	0.0164 (16)	0.0172 (17)	0.0024 (13)	0.0023 (15)	0.0000 (13)
C6	0.0201 (18)	0.0152 (16)	0.0193 (16)	0.0007 (12)	−0.0037 (14)	0.0010 (13)
C7	0.022 (2)	0.0162 (16)	0.0213 (18)	0.0031 (14)	−0.0021 (16)	−0.0008 (14)
C8	0.019 (2)	0.0206 (19)	0.0172 (17)	−0.0005 (14)	−0.0021 (16)	−0.0015 (14)
C9	0.023 (2)	0.0154 (17)	0.0144 (16)	−0.0014 (14)	0.0000 (15)	−0.0011 (13)
C10	0.019 (2)	0.0135 (16)	0.0152 (17)	−0.0028 (13)	0.0016 (16)	0.0000 (13)
C11	0.0184 (17)	0.0162 (16)	0.0161 (16)	−0.0003 (11)	0.0032 (14)	0.0000 (12)
C12	0.0224 (19)	0.0142 (14)	0.0147 (17)	−0.0013 (14)	0.0020 (14)	0.0001 (13)
C13	0.0182 (18)	0.0173 (16)	0.0143 (15)	−0.0001 (12)	−0.0001 (14)	−0.0003 (12)
C14	0.0177 (19)	0.0172 (16)	0.0170 (16)	−0.0024 (13)	0.0036 (14)	−0.0019 (13)
C15	0.0177 (19)	0.0157 (15)	0.0139 (16)	0.0004 (13)	0.0007 (14)	−0.0013 (13)
C16	0.016 (2)	0.040 (2)	0.029 (2)	−0.0035 (16)	0.0028 (17)	0.0044 (18)

Geometric parameters (Å, º)

Br—C4	1.892 (4)	C8—H8A	0.9500
S—C13	1.754 (4)	C9—C10	1.473 (7)
S—C16	1.798 (5)	C9—H9A	0.9500
O—C7	1.240 (5)	C10—C15	1.395 (6)
C1—C2	1.394 (6)	C10—C11	1.419 (5)
C1—C6	1.401 (5)	C11—C12	1.372 (6)
C1—C7	1.489 (6)	C11—H11A	0.9500
C2—C3	1.367 (6)	C12—C13	1.411 (5)
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.417 (5)	C13—C14	1.395 (5)
C3—H3A	0.9500	C14—C15	1.392 (6)
C4—C5	1.377 (6)	C14—H14A	0.9500
C5—C6	1.394 (6)	C15—H15A	0.9500
C5—H5A	0.9500	C16—H16A	0.9800
C6—H6A	0.9500	C16—H16B	0.9800
C7—C8	1.480 (6)	C16—H16C	0.9800
C8—C9	1.326 (6)
C13—S—C16	102.6 (2)	C8—C9—H9A	116.5
C2—C1—C6	119.5 (4)	C10—C9—H9A	116.5
C2—C1—C7	119.2 (3)	C15—C10—C11	117.3 (4)
C6—C1—C7	121.2 (4)	C15—C10—C9	119.3 (3)
C3—C2—C1	121.2 (3)	C11—C10—C9	123.2 (4)
C3—C2—H2A	119.4	C12—C11—C10	121.1 (4)
C1—C2—H2A	119.4	C12—C11—H11A	119.4
C2—C3—C4	118.8 (4)	C10—C11—H11A	119.4
C2—C3—H3A	120.6	C11—C12—C13	120.6 (4)
C4—C3—H3A	120.6	C11—C12—H12A	119.7
C5—C4—C3	121.0 (4)	C13—C12—H12A	119.7
C5—C4—Br	119.2 (3)	C14—C13—C12	119.3 (4)
C3—C4—Br	119.7 (3)	C14—C13—S	123.9 (3)
C4—C5—C6	119.4 (4)	C12—C13—S	116.9 (3)
C4—C5—H5A	120.3	C15—C14—C13	119.4 (4)
C6—C5—H5A	120.3	C15—C14—H14A	120.3
C5—C6—C1	120.0 (4)	C13—C14—H14A	120.3
C5—C6—H6A	120.0	C14—C15—C10	122.4 (4)
C1—C6—H6A	120.0	C14—C15—H15A	118.8
O—C7—C8	121.6 (4)	C10—C15—H15A	118.8
O—C7—C1	119.5 (4)	S—C16—H16A	109.5
C8—C7—C1	118.9 (4)	S—C16—H16B	109.5
C9—C8—C7	119.4 (4)	H16A—C16—H16B	109.5
C9—C8—H8A	120.3	S—C16—H16C	109.5
C7—C8—H8A	120.3	H16A—C16—H16C	109.5
C8—C9—C10	126.9 (4)	H16B—C16—H16C	109.5
C6—C1—C2—C3	0.0 (5)	C7—C8—C9—C10	174.5 (3)
C7—C1—C2—C3	177.2 (3)	C8—C9—C10—C15	178.7 (4)
C1—C2—C3—C4	−1.5 (5)	C8—C9—C10—C11	−5.6 (6)
C2—C3—C4—C5	1.7 (5)	C15—C10—C11—C12	1.2 (5)
C2—C3—C4—Br	179.9 (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—S	179.7 (3)
C2—C1—C6—C5	1.4 (5)	C16—S—C13—C14	4.9 (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—C15	0.9 (5)
C6—C1—C7—O	155.0 (4)	S—C13—C14—C15	−179.2 (3)
C2—C1—C7—C8	159.0 (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—C14	175.1 (3)
C1—C7—C8—C9	159.8 (3)