(2E)-1-(3-Bromo-2-thien­yl)-3-(4-methoxy­phen­yl)prop-2-en-1-one

Harrison, W.T.A.; Yathirajan, H.S.; Ashalatha, B.V.; Bindya, S.; Narayana, B.

doi:10.1107/S1600536806033824

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 9| September 2006| Pages o4164-o4165

https://doi.org/10.1107/S1600536806033824

(2E)-1-(3-Bromo-2-thienyl)-3-(4-methoxyphenyl)prop-2-en-1-one

William T. A. Harrison,^a ^* H. S. Yathirajan,^b B. V. Ashalatha,^c S. Bindya ^d and B. Narayana ^c

^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, and ^dDepartment of Chemistry, Sri Jayachamarajendra College of Engineering, Mysore 570 006, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 22 August 2006; accepted 22 August 2006; online 31 August 2006)

The molecules of the title compound, C₁₄H₁₁BrO₂S, display some distorted geometrical values that may be ascribed to an H⋯Br close contact. In the crystal structure, the molecules form translation-symmetry-generated infinite chains by way of a C—H⋯O interaction.

Comment

Chalcones and their heterocyclic derivatives show numerous biological effects (Opletalova & Sedivy, 1999 ). As part of our ongoing studies of these types of chalcones (Harrison et al., 2006 ; Yathirajan et al., 2006 ), the synthesis and structure of the title compound, (I) (Fig. 1), are presented here.

The bond lengths and angles in (I) mostly fall within their expected ranges (Cambridge Structural Database, Version 5.27; Allen, 2002 ). The terminal C14 methyl group is almost coplanar with its adjacent C8–C13 benzene ring mean plane [deviation of C14 = 0.015 (5) Å]. The dihedral angle between the C8–C13 benzene ring and C1–C4/S1 thiophene ring is 19.58 (9)°. The C5=O1 carbonyl group is also twisted with respect to the heterocycle, as reflected in the S1—C4—C5—O1 and C3—C4—C5—O1 torsion angles of −15.9 (3) and 164.0 (3)°, respectively.

The C3—C4—C5 angle of 135.8 (2)° is far more obtuse than the S1—C4—C5 angle of 114.52 (18)°, possibly as a result of a close intramolecular contact between Br1 and H6 (attached to C6): the separation of these atoms in (I) is 2.73 Å compared to the expected Bondi (1964 ) van der Waals separation of 3.05 Å. We presume that this represents a steric repulsion between Br and H rather than a C—H⋯Br `bond'. The difference between the C4—C3—Br1 and C2—C3—Br1 bond angles [126.74 (18) and 119.08 (18)°, respectively] might also reflect this repulsive contact. Similar angular distortions have been seen in other 4-bromothiophenes such as 4-(4-bromo-5-methylthiophen-2-yl)pyridine (Xu et al., 2005 ) and 3,4′-dibromo-2,2′-bithiophene (Antolini et al., 1997 ).

The crystal packing in (I) is consolidated by C1—H1⋯O2ⁱ interactions (Table 1) that link the molecules into chains propagating in [001]. A slightly short Br1⋯O2ⁱⁱ [symmetry code: (ii) 1-x, $[{1\over 2}]$ + y, 1-z] contact of 3.2184 (18) Å arises; the expected Bondi separation is 3.37 Å.

Figure 1
View of (I) showing 50% displacement ellipsoids and arbitrary spheres for the H atoms.

Figure 2
Unit-cell packing in (I), with all H atoms except H1 omitted for clarity and C—H⋯O interactions indicated by dashed lines. Atoms with an asterisk (*) are generated by the symmetry operation (x, y, z + 1).

Experimental

3-Bromo-2-acetylthiophene (10 g, 0.048 mol) in methanol (50 ml) was mixed with 4-methoxybenzaldehyde (6.52 g, 0.048 mol) and the mixture was treated with 10 ml of 30% potassium hydroxide solution at 278 K. The reaction mixture was then brought to room temperature and stirred for 3 h. The precipitated solid was filtered and washed with water, dried and recrytallized from acetone to yield light yellow crystals of (I) (yield 80%; m.p. 383 K).

Crystal data

C₁₄H₁₁BrO₂S
M_r = 323.20
Monoclinic, P 2₁
a = 4.0025 (1) Å
b = 10.7048 (3) Å
c = 14.6451 (5) Å
β = 91.789 (2)°
V = 627.18 (3) Å³
Z = 2
D_x = 1.711 Mg m⁻³
Mo Kα radiation
μ = 3.43 mm⁻¹
T = 120 (2) K
Slab, yellow
0.34 × 0.18 × 0.07 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.388, T_max = 0.795
7197 measured reflections
2705 independent reflections
2555 reflections with I > 2σ(I)
R_int = 0.024
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.056
S = 1.08
2705 reflections
165 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + 0.0736P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.55 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.016 (2)
Absolute structure: Flack (1983 ), 1198 Friedel pairs
Flack parameter: 0.013 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2ⁱ	0.95	2.54	3.457 (3)	162
Symmetry code: (i) x, y, z-1.

The H atoms were placed in idealized locations (C—H = 0.95–0.99 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The methyl group was rotated about its C—O bond 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/S1600536806033824/bg2004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806033824/bg2004Isup2.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-(3-Bromo-2-thienyl)-3-(4-methoxyphenyl)prop-2-en-1-one top

Crystal data top

C₁₄H₁₁BrO₂S	F(000) = 324
M_r = 323.20	D_x = 1.711 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1442 reflections
a = 4.0025 (1) Å	θ = 1.0–27.5°
b = 10.7048 (3) Å	µ = 3.43 mm⁻¹
c = 14.6451 (5) Å	T = 120 K
β = 91.789 (2)°	Slab, yellow
V = 627.18 (3) Å³	0.34 × 0.18 × 0.07 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	2705 independent reflections
Radiation source: fine-focus sealed tube	2555 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
φ and ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −5→5
T_min = 0.388, T_max = 0.795	k = −13→13
7197 measured reflections	l = −18→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + 0.0736P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.056	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.70 e Å⁻³
2705 reflections	Δρ_min = −0.55 e Å⁻³
165 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.016 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1198 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.013 (7)

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	0.2423 (6)	−0.0427 (2)	−0.04736 (17)	0.0193 (5)
H1	0.2683	−0.0523	−0.1112	0.023*
C2	0.3344 (6)	0.0614 (2)	−0.00015 (17)	0.0184 (5)
H2	0.4282	0.1337	−0.0269	0.022*
C3	0.2730 (6)	0.0486 (2)	0.09375 (16)	0.0164 (5)
C4	0.1342 (5)	−0.0634 (2)	0.11667 (16)	0.0156 (5)
C5	0.0263 (6)	−0.1228 (2)	0.20151 (18)	0.0207 (5)
C6	0.1591 (6)	−0.0777 (3)	0.29061 (18)	0.0224 (5)
H6	0.3067	−0.0082	0.2934	0.027*
C7	0.0716 (6)	−0.1346 (2)	0.36740 (18)	0.0221 (5)
H7	−0.0866	−0.2004	0.3608	0.026*
C8	0.1923 (6)	−0.1069 (2)	0.46063 (18)	0.0205 (5)
C9	0.3797 (6)	−0.0006 (2)	0.48433 (18)	0.0220 (5)
H9	0.4361	0.0566	0.4376	0.026*
C10	0.4853 (6)	0.0241 (2)	0.57303 (18)	0.0221 (5)
H10	0.6066	0.0981	0.5875	0.027*
C11	0.4104 (6)	−0.0621 (3)	0.64133 (18)	0.0194 (5)
C12	0.2243 (6)	−0.1685 (2)	0.62022 (18)	0.0207 (6)
H12	0.1722	−0.2264	0.6668	0.025*
C13	0.1154 (6)	−0.1897 (2)	0.53092 (17)	0.0215 (5)
H13	−0.0144	−0.2619	0.5171	0.026*
C14	0.6933 (6)	0.0627 (3)	0.75581 (19)	0.0251 (6)
H14A	0.7517	0.0604	0.8213	0.038*
H14B	0.5541	0.1361	0.7424	0.038*
H14C	0.8979	0.0673	0.7209	0.038*
O1	−0.1577 (5)	−0.2146 (2)	0.19520 (14)	0.0293 (4)
O2	0.5115 (4)	−0.04857 (17)	0.73066 (12)	0.0252 (4)
S1	0.07572 (15)	−0.15396 (5)	0.01985 (4)	0.01747 (14)
Br1	0.36561 (5)	0.18455 (3)	0.172837 (14)	0.02187 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0257 (12)	0.0204 (12)	0.0121 (12)	0.0067 (10)	0.0037 (9)	0.0018 (10)
C2	0.0190 (11)	0.0179 (12)	0.0186 (13)	0.0024 (9)	0.0038 (9)	0.0024 (10)
C3	0.0173 (11)	0.0168 (12)	0.0148 (12)	0.0011 (9)	−0.0026 (9)	−0.0016 (10)
C4	0.0170 (10)	0.0155 (12)	0.0141 (12)	0.0008 (9)	−0.0026 (9)	−0.0009 (10)
C5	0.0266 (12)	0.0185 (13)	0.0170 (14)	0.0042 (10)	0.0006 (10)	0.0034 (10)
C6	0.0241 (12)	0.0245 (13)	0.0187 (14)	−0.0001 (11)	−0.0002 (10)	0.0014 (11)
C7	0.0230 (12)	0.0225 (13)	0.0207 (15)	0.0009 (11)	0.0004 (10)	0.0005 (11)
C8	0.0238 (12)	0.0227 (13)	0.0153 (13)	0.0068 (10)	0.0045 (10)	0.0018 (10)
C9	0.0245 (12)	0.0196 (13)	0.0223 (14)	0.0048 (10)	0.0068 (10)	0.0077 (11)
C10	0.0205 (11)	0.0201 (12)	0.0260 (15)	0.0002 (11)	0.0036 (10)	0.0050 (11)
C11	0.0167 (10)	0.0250 (13)	0.0167 (13)	0.0062 (10)	0.0046 (9)	0.0042 (11)
C12	0.0201 (12)	0.0251 (14)	0.0172 (14)	0.0040 (10)	0.0041 (10)	0.0100 (11)
C13	0.0259 (12)	0.0182 (12)	0.0206 (14)	0.0021 (10)	0.0041 (10)	0.0034 (10)
C14	0.0216 (12)	0.0295 (14)	0.0240 (15)	0.0039 (11)	−0.0014 (10)	−0.0022 (11)
O1	0.0318 (10)	0.0298 (11)	0.0262 (11)	−0.0097 (8)	0.0006 (8)	0.0079 (9)
O2	0.0282 (9)	0.0273 (10)	0.0199 (10)	−0.0009 (8)	−0.0034 (7)	0.0036 (8)
S1	0.0220 (3)	0.0143 (3)	0.0159 (3)	−0.0006 (2)	−0.0015 (2)	−0.0022 (2)
Br1	0.02817 (13)	0.01867 (13)	0.01862 (14)	−0.00414 (12)	−0.00191 (8)	−0.00505 (12)

Geometric parameters (Å, º) top

C1—C2	1.357 (4)	C8—C13	1.400 (4)
C1—S1	1.695 (3)	C8—C9	1.401 (4)
C1—H1	0.9500	C9—C10	1.379 (4)
C2—C3	1.411 (3)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.400 (4)
C3—C4	1.368 (3)	C10—H10	0.9500
C3—Br1	1.889 (2)	C11—O2	1.365 (3)
C4—C5	1.472 (3)	C11—C12	1.390 (4)
C4—S1	1.727 (2)	C12—C13	1.384 (4)
C5—O1	1.230 (3)	C12—H12	0.9500
C5—C6	1.475 (4)	C13—H13	0.9500
C6—C7	1.335 (4)	C14—O2	1.437 (3)
C6—H6	0.9500	C14—H14A	0.9800
C7—C8	1.464 (4)	C14—H14B	0.9800
C7—H7	0.9500	C14—H14C	0.9800

C2—C1—S1	112.75 (19)	C10—C9—C8	122.3 (2)
C2—C1—H1	123.6	C10—C9—H9	118.8
S1—C1—H1	123.6	C8—C9—H9	118.8
C1—C2—C3	111.4 (2)	C9—C10—C11	118.8 (2)
C1—C2—H2	124.3	C9—C10—H10	120.6
C3—C2—H2	124.3	C11—C10—H10	120.6
C4—C3—C2	114.1 (2)	O2—C11—C12	116.2 (2)
C4—C3—Br1	126.74 (18)	O2—C11—C10	123.4 (2)
C2—C3—Br1	119.08 (18)	C12—C11—C10	120.4 (2)
C3—C4—C5	135.8 (2)	C13—C12—C11	119.7 (2)
C3—C4—S1	109.64 (18)	C13—C12—H12	120.2
C5—C4—S1	114.52 (18)	C11—C12—H12	120.2
O1—C5—C4	118.2 (2)	C12—C13—C8	121.4 (2)
O1—C5—C6	121.8 (2)	C12—C13—H13	119.3
C4—C5—C6	119.9 (2)	C8—C13—H13	119.3
C7—C6—C5	119.9 (3)	O2—C14—H14A	109.5
C7—C6—H6	120.0	O2—C14—H14B	109.5
C5—C6—H6	120.0	H14A—C14—H14B	109.5
C6—C7—C8	127.2 (3)	O2—C14—H14C	109.5
C6—C7—H7	116.4	H14A—C14—H14C	109.5
C8—C7—H7	116.4	H14B—C14—H14C	109.5
C13—C8—C9	117.4 (2)	C11—O2—C14	117.8 (2)
C13—C8—C7	118.9 (2)	C1—S1—C4	92.12 (12)
C9—C8—C7	123.6 (2)

S1—C1—C2—C3	1.2 (3)	C13—C8—C9—C10	−0.4 (3)
C1—C2—C3—C4	−0.4 (3)	C7—C8—C9—C10	178.9 (2)
C1—C2—C3—Br1	−177.62 (17)	C8—C9—C10—C11	1.8 (4)
C2—C3—C4—C5	179.6 (2)	C9—C10—C11—O2	178.0 (2)
Br1—C3—C4—C5	−3.5 (4)	C9—C10—C11—C12	−1.9 (3)
C2—C3—C4—S1	−0.5 (3)	O2—C11—C12—C13	−179.3 (2)
Br1—C3—C4—S1	176.42 (13)	C10—C11—C12—C13	0.6 (4)
C3—C4—C5—O1	164.0 (3)	C11—C12—C13—C8	0.9 (4)
S1—C4—C5—O1	−15.9 (3)	C9—C8—C13—C12	−1.0 (3)
C3—C4—C5—C6	−20.6 (4)	C7—C8—C13—C12	179.7 (2)
S1—C4—C5—C6	159.54 (18)	C12—C11—O2—C14	−177.6 (2)
O1—C5—C6—C7	−2.1 (4)	C10—C11—O2—C14	2.5 (3)
C4—C5—C6—C7	−177.4 (2)	C2—C1—S1—C4	−1.29 (19)
C5—C6—C7—C8	176.5 (2)	C3—C4—S1—C1	1.00 (18)
C6—C7—C8—C13	−169.4 (3)	C5—C4—S1—C1	−179.08 (18)
C6—C7—C8—C9	11.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2ⁱ	0.95	2.54	3.457 (3)	162

Symmetry code: (i) x, y, z−1.

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for data collection.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Antolini, L., Goldoni, F., Iarossi, D., Mucci, A. & Schenetti, L. (1997). J. Chem. Soc. Perkin Trans. 1, pp. 1957–1961. CrossRef Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harrison, W. T. A., Yathirajan, H. S., Sarojini, B. K., Narayana, B. & Vijaya Raj, K. K. (2006). Acta Cryst. E62, o1578–o1579. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Opletalova, V. & Sedivy, D. (1999). Ceska Slov. Farm. 48, 252–255. PubMed CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Xu, F., Chen, Z., Zhang, F., Wang, R.-J. & Zhao, F. (2005). Acta Cryst. E61, o1672–o1673. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yathirajan, H. S., Sarojini, B. K., Bindya, S., Narayana, B. & Bolte, M. (2006). Acta Cryst. E62, o4046–o4047. Web of Science CSD CrossRef IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.