(2E)-3-(Biphenyl-4-yl)-1-(3-bromo-2-thien­yl)prop-2-en-1-one

In the title compound, C₁₉H₁₃BrOS, the dihedral angles between the enone fragment and its adjacent thienyl (th) and phenyl­ene (bz) rings are 8.0 (2) and 12.8 (2)°, respectively. The dihedral angle between the th and bz rings is 19.9 (2)° and that between the two rings of the biphenyl fragment is 28.49 (18)°. A C—H...O inter­action may help to consolidate the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.046
• wR factor = 0.139
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.82
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.65
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C1      ..       5.58 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C2      ..       5.90 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C1

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      0.818
            Tmax scaled      0.334 Tmin scaled      0.275

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

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

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S1. Comment

The title compound, (I), (Fig. 1), was prepared as part of our ongoing studies (Harrison et al., 2006; Butcher et al., 2007) of the non-linear optical (NLO) properties (Uchida et al., 1998) and crystal structures of chalcone derivatives. Chalcones also display a wide variety of pharmacological effects (Dimmock et al., 1999). Compound (I) is centrosymmetric, thus its second harmonic generation (SHG) response is zero.

The geometrical parameters for (I) mostly fall within their expected ranges (Allen et al., 1995). The C4—C3—Br1 angle of 127.0 (3)° is somewhat obtuse, perhaps due to steric repulsion between Br1 and H6 (H···Br = 2.69 Å). The dihedral angles between the enone (C5/C6/C7/O1) fragment and its adjacent thienyl (C1–C4/S1) and benzne (C8–C13) rings are 8.0 (2)° and 12.8 (2)°, respectively. The dihedral angle between the thienyl and C8—C13 benzne ring systems is 19.9 (2)° and the dihedral angle between the two benzene ring planes (C8–C13 and C14–C19) of the biphenyl fragment is 28.49 (18)°. A possible weak intermolecular C—H···O interaction (Table 1) resulting in [001] chains of molecules may help to establish the crystal packing in (I).

Related literature

For general background, see: Uchida et al. (1998); Dimmock et al. (1999). For related structures, see: Butcher et al. (2007); Harrison et al. (2006). For reference structural data, see: Allen et al. (1995).

S2. Experimental

Biphenyl-4-carbaldehyde (1.82 g, 0.01 mol) in ethanol (30 ml) was mixed with 1-(3-bromo-2-thienyl)ethanone (2.05 ml, 0.01 mol) and the mixture was treated with 7 ml of 10% aqueous KOH and stirred for 8 h. The precipitate obtained was filtered, washed with ethanol and dried. Colourless chunks of (I) were recrystallized from ethyl acetate (m.p.: 404–406 K). Analysis for C₁₉H₁₃BrOS: Found (calculated): C 61.71 (61.80); H 3.49 (3.55); S 8.61% (8.68%).

S3. Refinement

The rather large, anisotropic displacement ellipsoids of C1, C2 and S1 are suggestive of disorder, but attempts to model this were not successful. The hydrogen atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.

Figures

Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).

(2E)-3-(Biphenyl-4-yl)-1-(3-bromo-2-thienyl)prop-2-en-1-one

Crystal data

C19H13BrOS	F(000) = 744
Mr = 369.26	Dx = 1.556 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3780 reflections
a = 8.8345 (5) Å	θ = 2.3–26.0°
b = 11.7429 (6) Å	µ = 2.74 mm^−1
c = 15.2162 (8) Å	T = 291 K
β = 92.817 (1)°	Chunk, colourless
V = 1576.66 (15) Å^3	0.51 × 0.40 × 0.40 mm
Z = 4

Data collection

Bruker SMART1000 CCD diffractometer	3101 independent reflections
Radiation source: fine-focus sealed tube	2252 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→10
Tmin = 0.336, Tmax = 0.409	k = −13→14
9060 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0796P)^2 + 0.7492P] where P = (Fo^2 + 2Fc^2)/3
3101 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 1.63 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

Special details

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
C1	0.2215 (7)	−0.1259 (4)	0.3559 (4)	0.0859 (18)
H1	0.1736	−0.1909	0.3334	0.103*
C2	0.1833 (5)	−0.0763 (4)	0.4308 (4)	0.0673 (13)
H2	0.1066	−0.1015	0.4658	0.081*
C3	0.2759 (4)	0.0202 (3)	0.4495 (3)	0.0528 (10)
C4	0.3794 (4)	0.0426 (3)	0.3897 (3)	0.0470 (9)
C5	0.4951 (4)	0.1313 (3)	0.3766 (3)	0.0456 (9)
C6	0.5326 (4)	0.2158 (3)	0.4463 (2)	0.0437 (8)
H6	0.4967	0.2059	0.5023	0.052*
C7	0.6174 (4)	0.3059 (3)	0.4292 (2)	0.0431 (8)
H7	0.6468	0.3120	0.3715	0.052*
C8	0.6705 (4)	0.3961 (3)	0.4883 (2)	0.0382 (7)
C9	0.6416 (4)	0.4009 (3)	0.5778 (2)	0.0413 (8)
H9	0.5830	0.3443	0.6021	0.050*
C10	0.6981 (4)	0.4878 (3)	0.6306 (2)	0.0401 (8)
H10	0.6769	0.4885	0.6899	0.048*
C11	0.7865 (4)	0.5750 (3)	0.5974 (2)	0.0360 (7)
C12	0.8154 (5)	0.5704 (3)	0.5082 (2)	0.0448 (8)
H12	0.8736	0.6271	0.4837	0.054*
C13	0.7589 (4)	0.4833 (3)	0.4558 (2)	0.0470 (9)
H13	0.7804	0.4826	0.3966	0.056*
C14	0.8449 (4)	0.6702 (3)	0.6537 (2)	0.0372 (7)
C15	0.7666 (5)	0.7065 (3)	0.7262 (2)	0.0466 (9)
H15	0.6784	0.6689	0.7404	0.056*
C16	0.8182 (5)	0.7973 (4)	0.7770 (3)	0.0554 (10)
H16	0.7641	0.8204	0.8248	0.066*
C17	0.9485 (5)	0.8537 (4)	0.7576 (3)	0.0567 (10)
H17	0.9829	0.9145	0.7922	0.068*
C18	1.0277 (5)	0.8198 (3)	0.6869 (3)	0.0556 (10)
H18	1.1160	0.8578	0.6735	0.067*
C19	0.9766 (4)	0.7292 (3)	0.6353 (3)	0.0482 (9)
H19	1.0313	0.7072	0.5875	0.058*
O1	0.5569 (4)	0.1320 (3)	0.3065 (2)	0.0685 (9)
S1	0.36513 (15)	−0.06020 (11)	0.30495 (8)	0.0698 (4)
Br1	0.24246 (5)	0.10336 (4)	0.55286 (3)	0.0651 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.084 (4)	0.046 (3)	0.124 (5)	−0.013 (2)	−0.048 (3)	−0.003 (3)
C2	0.058 (3)	0.050 (3)	0.092 (4)	−0.014 (2)	−0.021 (2)	0.008 (3)
C3	0.045 (2)	0.043 (2)	0.069 (3)	0.0021 (17)	−0.0107 (18)	0.0043 (19)
C4	0.043 (2)	0.034 (2)	0.062 (2)	0.0016 (15)	−0.0115 (17)	−0.0055 (17)
C5	0.040 (2)	0.038 (2)	0.057 (2)	0.0045 (15)	−0.0042 (16)	−0.0086 (16)
C6	0.0443 (19)	0.044 (2)	0.0432 (18)	−0.0037 (16)	0.0030 (15)	−0.0050 (16)
C7	0.051 (2)	0.0366 (19)	0.0422 (18)	0.0025 (16)	0.0033 (15)	−0.0012 (15)
C8	0.0426 (19)	0.0294 (17)	0.0425 (18)	0.0002 (14)	0.0022 (14)	0.0017 (14)
C9	0.0446 (19)	0.0345 (19)	0.0455 (19)	−0.0039 (15)	0.0081 (15)	0.0050 (15)
C10	0.0459 (19)	0.0381 (19)	0.0370 (17)	−0.0006 (15)	0.0073 (14)	0.0029 (15)
C11	0.0393 (18)	0.0284 (16)	0.0403 (17)	0.0036 (13)	0.0008 (14)	0.0045 (13)
C12	0.061 (2)	0.0329 (18)	0.0415 (18)	−0.0087 (16)	0.0099 (16)	0.0048 (15)
C13	0.067 (2)	0.038 (2)	0.0363 (18)	−0.0060 (18)	0.0109 (16)	0.0004 (15)
C14	0.0434 (19)	0.0310 (18)	0.0366 (17)	0.0037 (14)	−0.0023 (14)	0.0032 (13)
C15	0.052 (2)	0.044 (2)	0.0435 (19)	−0.0034 (17)	0.0026 (16)	−0.0032 (16)
C16	0.070 (3)	0.052 (2)	0.044 (2)	0.001 (2)	0.0022 (18)	−0.0101 (18)
C17	0.067 (3)	0.041 (2)	0.060 (2)	0.000 (2)	−0.016 (2)	−0.0087 (19)
C18	0.050 (2)	0.045 (2)	0.071 (3)	−0.0093 (18)	−0.0031 (19)	−0.0020 (19)
C19	0.047 (2)	0.042 (2)	0.056 (2)	−0.0022 (17)	0.0067 (16)	−0.0041 (17)
O1	0.074 (2)	0.069 (2)	0.0636 (18)	−0.0089 (16)	0.0186 (16)	−0.0273 (15)
S1	0.0722 (8)	0.0585 (7)	0.0765 (8)	0.0023 (6)	−0.0177 (6)	−0.0149 (6)
Br1	0.0550 (3)	0.0701 (3)	0.0708 (3)	−0.0029 (2)	0.0100 (2)	0.0002 (2)

Geometric parameters (Å, º)

C1—C2	1.339 (8)	C10—C11	1.397 (5)
C1—S1	1.703 (7)	C10—H10	0.9300
C1—H1	0.9300	C11—C12	1.395 (5)
C2—C3	1.418 (6)	C11—C14	1.484 (5)
C2—H2	0.9300	C12—C13	1.376 (5)
C3—C4	1.348 (6)	C12—H12	0.9300
C3—Br1	1.887 (4)	C13—H13	0.9300
C4—C5	1.480 (5)	C14—C19	1.395 (5)
C4—S1	1.766 (4)	C14—C15	1.397 (5)
C5—O1	1.222 (5)	C15—C16	1.381 (5)
C5—C6	1.478 (5)	C15—H15	0.9300
C6—C7	1.330 (5)	C16—C17	1.373 (6)
C6—H6	0.9300	C16—H16	0.9300
C7—C8	1.452 (5)	C17—C18	1.371 (6)
C7—H7	0.9300	C17—H17	0.9300
C8—C13	1.393 (5)	C18—C19	1.384 (5)
C8—C9	1.399 (5)	C18—H18	0.9300
C9—C10	1.378 (5)	C19—H19	0.9300
C9—H9	0.9300
C2—C1—S1	114.5 (4)	C11—C10—H10	119.1
C2—C1—H1	122.7	C12—C11—C10	117.1 (3)
S1—C1—H1	122.7	C12—C11—C14	121.1 (3)
C1—C2—C3	110.6 (5)	C10—C11—C14	121.8 (3)
C1—C2—H2	124.7	C13—C12—C11	121.0 (3)
C3—C2—H2	124.7	C13—C12—H12	119.5
C4—C3—C2	115.1 (4)	C11—C12—H12	119.5
C4—C3—Br1	127.0 (3)	C12—C13—C8	122.3 (3)
C2—C3—Br1	117.9 (4)	C12—C13—H13	118.8
C3—C4—C5	136.4 (4)	C8—C13—H13	118.8
C3—C4—S1	109.5 (3)	C19—C14—C15	117.2 (3)
C5—C4—S1	114.1 (3)	C19—C14—C11	121.9 (3)
O1—C5—C6	121.9 (4)	C15—C14—C11	120.9 (3)
O1—C5—C4	117.6 (3)	C16—C15—C14	121.0 (4)
C6—C5—C4	120.5 (3)	C16—C15—H15	119.5
C7—C6—C5	120.1 (3)	C14—C15—H15	119.5
C7—C6—H6	119.9	C17—C16—C15	120.6 (4)
C5—C6—H6	119.9	C17—C16—H16	119.7
C6—C7—C8	128.8 (3)	C15—C16—H16	119.7
C6—C7—H7	115.6	C18—C17—C16	119.6 (4)
C8—C7—H7	115.6	C18—C17—H17	120.2
C13—C8—C9	116.6 (3)	C16—C17—H17	120.2
C13—C8—C7	119.1 (3)	C17—C18—C19	120.2 (4)
C9—C8—C7	124.3 (3)	C17—C18—H18	119.9
C10—C9—C8	121.3 (3)	C19—C18—H18	119.9
C10—C9—H9	119.4	C18—C19—C14	121.4 (4)
C8—C9—H9	119.4	C18—C19—H19	119.3
C9—C10—C11	121.7 (3)	C14—C19—H19	119.3
C9—C10—H10	119.1	C1—S1—C4	90.3 (2)
S1—C1—C2—C3	−0.7 (5)	C10—C11—C12—C13	−0.1 (5)
C1—C2—C3—C4	0.7 (6)	C14—C11—C12—C13	−178.8 (3)
C1—C2—C3—Br1	−179.7 (3)	C11—C12—C13—C8	0.2 (6)
C2—C3—C4—C5	177.4 (4)	C9—C8—C13—C12	−0.1 (6)
Br1—C3—C4—C5	−2.1 (7)	C7—C8—C13—C12	−178.9 (4)
C2—C3—C4—S1	−0.4 (4)	C12—C11—C14—C19	−28.0 (5)
Br1—C3—C4—S1	−179.9 (2)	C10—C11—C14—C19	153.3 (3)
C3—C4—C5—O1	−170.5 (4)	C12—C11—C14—C15	150.0 (4)
S1—C4—C5—O1	7.2 (5)	C10—C11—C14—C15	−28.6 (5)
C3—C4—C5—C6	9.1 (7)	C19—C14—C15—C16	0.1 (5)
S1—C4—C5—C6	−173.2 (3)	C11—C14—C15—C16	−178.0 (3)
O1—C5—C6—C7	10.7 (6)	C14—C15—C16—C17	−0.3 (6)
C4—C5—C6—C7	−169.0 (3)	C15—C16—C17—C18	0.3 (6)
C5—C6—C7—C8	−178.0 (3)	C16—C17—C18—C19	0.0 (6)
C6—C7—C8—C13	−179.9 (4)	C17—C18—C19—C14	−0.2 (6)
C6—C7—C8—C9	1.5 (6)	C15—C14—C19—C18	0.1 (5)
C13—C8—C9—C10	0.0 (5)	C11—C14—C19—C18	178.2 (3)
C7—C8—C9—C10	178.6 (3)	C2—C1—S1—C4	0.4 (4)
C8—C9—C10—C11	0.1 (5)	C3—C4—S1—C1	0.0 (3)
C9—C10—C11—C12	0.0 (5)	C5—C4—S1—C1	−178.3 (3)
C9—C10—C11—C14	178.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1^i	0.93	2.54	3.321 (5)	142

Symmetry code: (i) x, −y+1/2, z+1/2.