1-(3-Bromo-2-thien­yl)ethanone

Mahendra, M.; Vivek, H.K.; Gaonkar, S.L.; Priya, B.S.; Nanjunda Swamy, S.

doi:10.1107/S1600536810034677

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2540

doi:10.1107/S1600536810034677

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1-(3-Bromo-2-thienyl)ethanone

M. Mahendra,^a H. K. Vivek,^b S. L. Gaonkar,^c B. S. Priya ^c and S. Nanjunda Swamy ^b ^*

^aDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Biotechnology, Sri Jayachamarajendra College of Engineering, Mysore 570 006, India, and ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India
^*Correspondence e-mail: nanju_xrd@yahoo.com

(Received 19 August 2010; accepted 28 August 2010; online 11 September 2010)

In the title compound, C₆H₅BrOS, the non-H and aromatic H atoms lie on a crystallographic mirror plane. In the crystal, molecules are linked into chains propagating along the c axis by intermolecular C—H⋯O hydrogen bonds.

Related literature

For the uses of acetyl thiophenes, see: Ashalatha et al. (2009 ); Bando et al. (2010 ); Ito & Furukawa (1990 ); Lutz et al. (2005 ); Nakayama et al. (1989 ); Pelly et al. (2005 ); Yasuhara et al. (2002 ).

Experimental

Crystal data

C₆H₅BrOS
M_r = 205.07
Orthorhombic, C m c a
a = 6.8263 (17) Å
b = 13.149 (4) Å
c = 16.007 (4) Å
V = 1436.8 (7) Å³
Z = 8
Mo Kα radiation
μ = 5.92 mm⁻¹
T = 293 K
0.25 × 0.21 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.313, T_max = 0.384
12363 measured reflections
973 independent reflections
790 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.067
S = 1.06
973 reflections
56 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O8ⁱ	0.93	2.43	3.352 (4)	174
Symmetry code: (i) $[-x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810034677/ci5166sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034677/ci5166Isup2.hkl

checkCIF report

Comment top

2-Acetyl-3-bromothiophene is one of the well-known bio-active intermediate used for the construction of number of new heterocycles (Lutz et al. 2005; Pelly et al. 2005). It is used as an intermediate for the synthesis of furo[3,2-a]carbazole alkaloid, furostifoline (Ito et al. 1990) and its derivatives, which show broad pharmacological properties (Yasuhara et al. 2002). Chalcones of 2-acetyl-3-bromothiophene exhibit promising anti-inflammatory, analgesic and antibacterial activities (Ashalatha et al. 2009). Acetyl thiophenes are useful as intermediates for preparing number of pharmaceutical compounds (Bando et al. 2010). Acetyl bromothiophenes are also used for the synthesis of number of biologically active pyridazine derivatives (Nakayama et al. 1989). With this background, the title compound (I), was synthesized and we report its crystal structure here.

The non-hydrogen and aromatic hydrogen atoms of the title molecule lie on a crystallographic mirror plane (Fig. 1). The molecules are linked into a chain along the c axis by intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For the uses of acetyl thiophenes, see: Ashalatha et al. (2009); Bando et al. (2010); Ito & Furukawa (1990); Lutz et al. (2005); Nakayama et al. (1989); Pelly et al. (2005); Yasuhara et al. (2002).

Experimental top

A three-necked, round-bottomed flask was charged with CH₂Cl₂ (10 ml) and anhydrous AlCl₃ (2.45 g, 18.4 mmol). The flask was cooled to 273 K. A dropping funnel was charged with freshly distilled acetyl chloride (1.48 g, 19.6 mmol) in CH₂Cl₂ (15 ml), and was added drop wise for a period of 30 min. The reaction mixture was stirred for 1 h at 273 K. The reaction mass was further cooled to 250 K. 3-Bromothiophene (1.00 g, 6.13 mmol) in CH₂Cl₂ (15 mL) was added drop wise for 1 h. The reaction was stirred at 250 K for 30 min and then warmed slowly to room temperature and stirred for 1 h. Then the reaction mixture was quenched on ice water (50 ml). Layers were separated and aqueous layer was repeatedly extracted with CH₂Cl₂ and the combined organic extracts were washed with saturated NaHCO₃ (25 ml), then brine (25 ml) and finally dried over anhydrous Na₂SO₄. Solvent was removed by distillation at atmospheric pressure. The remaining oily mass was distilled under high vacuum (403 K at 10 mbar) to give a pale yellow oil which was crystallized in n-hexane to give 2-acetyl-3-bromothiophene (1.10 g, 88 %) as a yellow solid. Block-shaped yellow single crystals were obtained by slow evaporation of an n-hexane solution.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of (I), showing 50% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. Packing diagram of (I), viewed down the a axis. The dashed lines represent hydrogen bonds.

1-(3-Bromo-2-thienyl)ethanone top

Crystal data top

C₆H₅BrOS	F(000) = 800
M_r = 205.07	D_x = 1.896 Mg m⁻³
Orthorhombic, Cmca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2bc 2	Cell parameters from 1982 reflections
a = 6.8263 (17) Å	θ = 2.5–28.4°
b = 13.149 (4) Å	µ = 5.92 mm⁻¹
c = 16.007 (4) Å	T = 293 K
V = 1436.8 (7) Å³	Block, yellow
Z = 8	0.25 × 0.21 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	973 independent reflections
Radiation source: fine-focus sealed tube	790 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ω and ϕ scans	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→9
T_min = 0.313, T_max = 0.384	k = −17→17
12363 measured reflections	l = −21→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0333P)² + 1.3829P] where P = (F_o² + 2F_c²)/3
973 reflections	(Δ/σ)_max = 0.001
56 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₆H₅BrOS	V = 1436.8 (7) Å³
M_r = 205.07	Z = 8
Orthorhombic, Cmca	Mo Kα radiation
a = 6.8263 (17) Å	µ = 5.92 mm⁻¹
b = 13.149 (4) Å	T = 293 K
c = 16.007 (4) Å	0.25 × 0.21 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	973 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	790 reflections with I > 2σ(I)
T_min = 0.313, T_max = 0.384	R_int = 0.041
12363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.06	Δρ_max = 0.68 e Å⁻³
973 reflections	Δρ_min = −0.48 e Å⁻³
56 parameters

Special details top

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	Occ. (<1)
Br1	0.00000	0.01659 (3)	0.38478 (2)	0.0547 (1)
S5	0.00000	0.33480 (6)	0.30339 (5)	0.0463 (3)
O8	0.00000	0.19098 (19)	0.51639 (13)	0.0584 (9)
C2	0.00000	0.1452 (2)	0.33378 (18)	0.0365 (9)
C3	0.00000	0.1547 (3)	0.2458 (2)	0.0448 (10)
C4	0.00000	0.2530 (3)	0.2207 (2)	0.0479 (10)
C6	0.00000	0.2366 (2)	0.37465 (17)	0.0357 (9)
C7	0.00000	0.2587 (2)	0.46527 (19)	0.0389 (9)
C9	0.00000	0.3685 (3)	0.4922 (2)	0.0541 (11)
H3	0.00000	0.09970	0.20930	0.0540*
H4	0.00000	0.27350	0.16510	0.0570*
H9A	0.13140	0.39450	0.49060	0.0810*	0.500
H9B	−0.05010	0.37360	0.54810	0.0810*	0.500
H9C	−0.08130	0.40740	0.45510	0.0810*	0.500

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0910 (3)	0.0316 (2)	0.0415 (2)	0.0000	0.0000	−0.0009 (1)
S5	0.0590 (5)	0.0401 (4)	0.0397 (4)	0.0000	0.0000	0.0117 (3)
O8	0.106 (2)	0.0408 (13)	0.0285 (12)	0.0000	0.0000	0.0023 (10)
C2	0.0400 (16)	0.0399 (16)	0.0297 (14)	0.0000	0.0000	0.0021 (12)
C3	0.0512 (18)	0.0519 (18)	0.0314 (15)	0.0000	0.0000	−0.0035 (13)
C4	0.0526 (19)	0.063 (2)	0.0281 (14)	0.0000	0.0000	0.0069 (14)
C6	0.0428 (16)	0.0333 (14)	0.0309 (15)	0.0000	0.0000	0.0057 (11)
C7	0.0482 (17)	0.0354 (15)	0.0332 (15)	0.0000	0.0000	−0.0021 (12)
C9	0.079 (2)	0.0385 (16)	0.0448 (19)	0.0000	0.0000	−0.0061 (14)

Geometric parameters (Å, º) top

Br1—C2	1.878 (3)	C3—H3	0.93
S5—C4	1.706 (4)	C4—H4	0.93
S5—C6	1.723 (3)	C9—H9A	0.96
O8—C7	1.209 (4)	C9—H9B	0.96
C2—C3	1.414 (4)	C9—H9C	0.96
C2—C6	1.368 (4)	C9—H9Aⁱ	0.96
C3—C4	1.354 (6)	C9—H9Bⁱ	0.96
C6—C7	1.479 (4)	C9—H9Cⁱ	0.96
C7—C9	1.507 (5)

Br1···O8	3.114 (3)	C3···C3^xi	3.4158 (11)
Br1···Br1ⁱⁱ	3.7144 (12)	C3···C3^ix	3.4158 (11)
Br1···O8ⁱⁱ	3.155 (3)	C3···C3^vi	3.4158 (11)
Br1···S5ⁱⁱⁱ	3.8453 (15)	C4···O8^xvi	3.352 (4)
Br1···Br1^iv	3.7144 (12)	C4···O8^xvii	3.352 (4)
Br1···O8^iv	3.155 (3)	C4···S5^x	3.5993 (17)
Br1···S5^v	3.8453 (15)	C4···S5^xi	3.5993 (17)
S5···C4^vi	3.5993 (17)	C4···C4^x	3.5397 (16)
S5···Br1^vii	3.8453 (15)	C4···C4^xi	3.5397 (16)
S5···Br1^viii	3.8453 (15)	C4···S5^ix	3.5993 (17)
S5···C4^ix	3.5993 (17)	C4···S5^vi	3.5993 (17)
S5···C4^x	3.5993 (17)	C4···C4^ix	3.5397 (16)
S5···C4^xi	3.5993 (17)	C4···C4^vi	3.5397 (16)
S5···H9Cⁱ	2.6700	C7···C7^xiv	3.5970 (17)
S5···H9C	2.6700	C7···C7^xviii	3.5970 (17)
O8···Br1	3.114 (3)	C7···C7^xix	3.5970 (17)
O8···C4^xii	3.352 (4)	C7···C7^xv	3.5970 (17)
O8···C4^xiii	3.352 (4)	C9···C9^xx	3.467 (6)
O8···Br1ⁱⁱ	3.155 (3)	C9···C9^xxi	3.467 (6)
O8···Br1^iv	3.155 (3)	H4···O8^xvi	2.4300
O8···H4^xii	2.4300	H4···O8^xvii	2.4300
O8···H4^xiii	2.4300	H9A···O8^xviii	2.7600
O8···H9A^xiv	2.7600	H9A···O8^xv	2.7600
O8···H9A^xv	2.7600	H9C···S5	2.6700
C3···C3^x	3.4158 (11)

C4—S5—C6	92.36 (16)	C7—C9—H9B	109.00
Br1—C2—C3	120.8 (2)	C7—C9—H9C	109.00
Br1—C2—C6	125.7 (2)	C7—C9—H9Aⁱ	109.00
C3—C2—C6	113.5 (3)	C7—C9—H9Bⁱ	109.00
C2—C3—C4	112.3 (3)	C7—C9—H9Cⁱ	109.00
S5—C4—C3	111.8 (2)	H9A—C9—H9B	109.00
S5—C6—C2	110.0 (2)	H9A—C9—H9C	109.00
S5—C6—C7	120.1 (2)	H9A—C9—H9Aⁱ	138.00
C2—C6—C7	129.9 (2)	H9A—C9—H9Bⁱ	71.00
O8—C7—C6	121.3 (3)	H9B—C9—H9C	109.00
O8—C7—C9	120.8 (3)	H9Aⁱ—C9—H9B	71.00
C6—C7—C9	118.0 (2)	H9B—C9—H9Cⁱ	138.00
C2—C3—H3	124.00	H9Bⁱ—C9—H9C	138.00
C4—C3—H3	124.00	H9C—C9—H9Cⁱ	71.00
S5—C4—H4	124.00	H9Aⁱ—C9—H9Bⁱ	109.00
C3—C4—H4	124.00	H9Aⁱ—C9—H9Cⁱ	109.00
C7—C9—H9A	109.00	H9Bⁱ—C9—H9Cⁱ	109.00

C6—S5—C4—C3	0.00	C3—C2—C6—S5	0.00
C4—S5—C6—C2	0.00	C3—C2—C6—C7	180.00
C4—S5—C6—C7	−180.00	C2—C3—C4—S5	0.00
Br1—C2—C3—C4	−180.00	S5—C6—C7—O8	−180.00
C6—C2—C3—C4	0.00	S5—C6—C7—C9	0.00
Br1—C2—C6—S5	180.00	C2—C6—C7—O8	0.00
Br1—C2—C6—C7	0.00	C2—C6—C7—C9	−180.00

Symmetry codes: (i) −x, y, z; (ii) x, −y, −z+1; (iii) −x, y−1/2, −z+1/2; (iv) −x, −y, −z+1; (v) x, y−1/2, −z+1/2; (vi) x+1/2, y, −z+1/2; (vii) −x, y+1/2, −z+1/2; (viii) x, y+1/2, −z+1/2; (ix) x−1/2, y, −z+1/2; (x) −x−1/2, y, −z+1/2; (xi) −x+1/2, y, −z+1/2; (xii) −x, −y+1/2, z+1/2; (xiii) x, −y+1/2, z+1/2; (xiv) x−1/2, −y+1/2, −z+1; (xv) −x+1/2, −y+1/2, −z+1; (xvi) −x, −y+1/2, z−1/2; (xvii) x, −y+1/2, z−1/2; (xviii) x+1/2, −y+1/2, −z+1; (xix) −x−1/2, −y+1/2, −z+1; (xx) x, −y+1, −z+1; (xxi) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O8^xvi	0.93	2.43	3.352 (4)	174

Symmetry code: (xvi) −x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅BrOS
M_r	205.07
Crystal system, space group	Orthorhombic, Cmca
Temperature (K)	293
a, b, c (Å)	6.8263 (17), 13.149 (4), 16.007 (4)
V (Å³)	1436.8 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.92
Crystal size (mm)	0.25 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.313, 0.384
No. of measured, independent and observed [I > 2σ(I)] reflections	12363, 973, 790
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.067, 1.06
No. of reflections	973
No. of parameters	56
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.48

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O8ⁱ	0.93	2.43	3.352 (4)	174

Symmetry code: (i) −x, −y+1/2, z−1/2.

Acknowledgements

SNS is grateful to University Grants Commission (UGC), Government of India, for financial support under the major research project [grant No. 38–220/2009 (SR)]. SNS also expresses his sincere gratitude to J. S. S. Mahavidyapeetha for the encouragement towards this research work. MM thanks the University of Mysore for awarding a project (No. DV3/136/2007–2008/24.09.09).

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