2-Bromo-2-methyl-1-[4-(methyl­sulfan­yl)phen­yl]propan-1-one

Liu, F.; Ren, S.-Y.; Yang, W.-J.

doi:10.1107/S1600536812021472

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1759

doi:10.1107/S1600536812021472

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2-Bromo-2-methyl-1-[4-(methylsulfanyl)phenyl]propan-1-one

Fei Liu,^a ^* Shi-Ying Ren ^a and Wei-Ji Yang ^b

^aSchool of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huai'an, 223003 Jiangsu Province, People's Republic of China, and ^bGraduate School, Zhejiang Chinese Medical University, Hangzhou, 310053, People's Republic of China
^*Correspondence e-mail: huanhailf@yahoo.com.cn

(Received 16 April 2012; accepted 11 May 2012; online 16 May 2012)

In the title compound, C₁₁H₁₃BrOS, the thioether unit and the phenyl ring adopt an essentially planar conformation, with a maximum deviation of 0.063 Å. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, extending in zigzag chains along the b axis. A weak intramolecular C—H⋯Br hydrogen bond is also observed, which forms an S(6) ring motif.

Related literature

For general background to the properties of the title compound, a key intermediate for the preparation of a UV initiator, and its synthesis, see: Zhao et al. (2010 ); Liu et al. (2010 ). For related structures, see: Anuradha et al. (2008 ); Moreno-Fuquen et al. (2011 ).

Experimental

Crystal data

C₁₁H₁₃BrOS
M_r = 273.18
Monoclinic, P 2₁ /n
a = 11.061 (3) Å
b = 7.120 (2) Å
c = 14.721 (4) Å
β = 97.638 (3)°
V = 1149.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.73 mm⁻¹
T = 153 K
0.27 × 0.23 × 0.18 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.433, T_max = 0.551
9900 measured reflections
3625 independent reflections
2901 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.073
S = 1.00
3625 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O1ⁱ	0.98	2.47	3.359 (2)	150
C5—H5⋯Br1	0.95	2.78	3.387 (2)	123
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812021472/bg2458sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021472/bg2458Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021472/bg2458Isup3.cml

checkCIF report

Comment top

The title compound is a key intermediate for the preparation of 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-propanone, which is used as a UV initiator (Zhao et al., 2010). It was prepared from thioanisole, which was reacted with isobutyryl chloride in the presence of aluminium cloride, followed by bromination with bromine/acetic acid (Liu et al., 2010).

C—S bond lengths and the C—S—C angle agree with those in (E)-3-(4-fluorophenyl)-1-[4-(methylsulfanyl)phenyl]prop-2-en-1-one (Anuradha et al., 2008). The S—Csp³ bond length (1.7954 Å) is longer than the S—Csp² one (1.7548 Å) and the C—Br distance length (1.9962 Å) is in the normal range for this type of bonds (Moreno-Fuquen et al., 2011).

The thioether moiety and phenyl ring adopt an essentially planar conformation with a maximum deviation of 0.063 Å (Fig. 1). In the crystal, molecules are linked by C—H···O hydrogen bonds, extending as zigzag chains along the b axis (Fig. 2). In addition, a weak intramolecular C—H···Br hydrogen bond is also observed, forming an S(6) ring motif. This H-bond geometry is listed in Table 1.

Related literature top

For general backgroud to the properties of the title compound, a key intermediate for the preparation of a UV initiator, and its synthesis, see: Zhao et al. (2010); Liu et al. (2010). For related structures, see: Anuradha et al. (2008); Moreno-Fuquen et al. (2011).

Experimental top

To a mixture of dichloroethane (50 ml) and aluminium cloride (17.4 g, 130 mmol) was added isobutyryl chloride (13.8 g, 130 mmol) at 298 K. Thioanisole (10.8 g, 100 mmol) was added dropwise to the mixture. After completion, it was poured into diluted hydrochloric acid and the organic layer was extracted.

To the organic layer, acetic acid (7.4 g, 123 mmol) and 30% hydrogen peroxide solution (7.4 g, 65 mmol) were added. Then, bromine (10.4 g, 65 mmol) was added at 303 K. After completion, water was added, and the organic layer was washed by 5% sodium bicarbonate solution and concentrated to yield the title compound with a yield of 77.3%. The crude product was recrystallized by slow evaporation from ethanol to give the single crystals used for data collection.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2008); cell refinement: CrystalClear (Rigaku/MSC, 2008); data reduction: CrystalClear (Rigaku/MSC, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The packing of the crystal structure of (I), showing the intramolecular hydrogen bonds and the zigzag chains formed by C—H···O hydrogen bonds (dotted lines).

2-Bromo-2-methyl-1-[4-(methylsulfanyl)phenyl]propan-1-one top

Crystal data top

C₁₁H₁₃BrOS	F(000) = 552
M_r = 273.18	D_x = 1.579 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4327 reflections
a = 11.061 (3) Å	θ = 2.2–31.0°
b = 7.120 (2) Å	µ = 3.73 mm⁻¹
c = 14.721 (4) Å	T = 153 K
β = 97.638 (3)°	Block, colourless
V = 1149.1 (5) Å³	0.27 × 0.23 × 0.18 mm
Z = 4

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	3625 independent reflections
Radiation source: Rotating Anode	2901 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 28.5714 pixels mm^-1	θ_max = 31.0°, θ_min = 2.8°
phi and ω scans	h = −16→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→8
T_min = 0.433, T_max = 0.551	l = −21→21
9900 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0339P)²] where P = (F_o² + 2F_c²)/3
3625 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

C₁₁H₁₃BrOS	V = 1149.1 (5) Å³
M_r = 273.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.061 (3) Å	µ = 3.73 mm⁻¹
b = 7.120 (2) Å	T = 153 K
c = 14.721 (4) Å	0.27 × 0.23 × 0.18 mm
β = 97.638 (3)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	3625 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2901 reflections with I > 2σ(I)
T_min = 0.433, T_max = 0.551	R_int = 0.033
9900 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.00	Δρ_max = 0.57 e Å⁻³
3625 reflections	Δρ_min = −0.72 e Å⁻³
130 parameters

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
Br1	0.327247 (17)	0.69311 (3)	0.037381 (13)	0.03062 (7)
S1	0.86419 (4)	0.48317 (6)	0.36691 (3)	0.02352 (10)
O1	0.25965 (11)	0.5378 (2)	0.26208 (9)	0.0358 (3)
C1	0.71222 (15)	0.4889 (2)	0.31441 (12)	0.0184 (3)
C2	0.62070 (15)	0.4850 (2)	0.37198 (12)	0.0211 (3)
H2	0.6426	0.4798	0.4366	0.025*
C3	0.49965 (15)	0.4886 (2)	0.33555 (12)	0.0213 (3)
H3	0.4389	0.4856	0.3755	0.026*
C4	0.46416 (15)	0.4968 (2)	0.24059 (11)	0.0186 (3)
C5	0.55563 (15)	0.5004 (2)	0.18392 (12)	0.0201 (3)
H5	0.5339	0.5061	0.1193	0.024*
C6	0.67786 (16)	0.4957 (2)	0.22041 (12)	0.0212 (3)
H6	0.7387	0.4972	0.1805	0.025*
C7	0.94956 (16)	0.4878 (3)	0.27138 (13)	0.0256 (4)
H7A	0.9245	0.3824	0.2303	0.031*
H7B	1.0368	0.4773	0.2937	0.031*
H7C	0.9340	0.6063	0.2380	0.031*
C8	0.33064 (16)	0.5063 (2)	0.20746 (12)	0.0214 (4)
C9	0.27806 (15)	0.4717 (2)	0.10720 (12)	0.0213 (4)
C10	0.13996 (16)	0.4720 (3)	0.09560 (14)	0.0325 (4)
H10A	0.1084	0.4581	0.0305	0.039*
H10B	0.1110	0.5908	0.1185	0.039*
H10C	0.1111	0.3673	0.1303	0.039*
C11	0.32472 (17)	0.2949 (2)	0.06566 (13)	0.0264 (4)
H11A	0.3003	0.1846	0.0987	0.032*
H11B	0.4139	0.2998	0.0705	0.032*
H11C	0.2900	0.2861	0.0010	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03163 (12)	0.03130 (13)	0.02925 (11)	0.00122 (8)	0.00520 (8)	0.00951 (8)
S1	0.0197 (2)	0.0277 (2)	0.0229 (2)	0.00113 (17)	0.00177 (16)	−0.00186 (17)
O1	0.0213 (7)	0.0622 (10)	0.0251 (7)	0.0015 (7)	0.0078 (5)	−0.0100 (7)
C1	0.0189 (8)	0.0163 (8)	0.0201 (8)	0.0003 (6)	0.0028 (6)	−0.0008 (6)
C2	0.0234 (9)	0.0247 (9)	0.0155 (8)	0.0015 (7)	0.0036 (6)	−0.0007 (6)
C3	0.0230 (8)	0.0229 (9)	0.0194 (8)	0.0001 (7)	0.0077 (6)	−0.0014 (7)
C4	0.0193 (8)	0.0178 (8)	0.0193 (8)	0.0004 (6)	0.0054 (6)	−0.0005 (6)
C5	0.0213 (8)	0.0240 (9)	0.0158 (8)	−0.0008 (7)	0.0060 (6)	−0.0001 (6)
C6	0.0218 (8)	0.0230 (9)	0.0204 (8)	−0.0011 (7)	0.0085 (6)	0.0001 (7)
C7	0.0187 (8)	0.0266 (10)	0.0323 (10)	−0.0008 (7)	0.0063 (7)	0.0006 (8)
C8	0.0207 (8)	0.0234 (9)	0.0209 (8)	0.0004 (7)	0.0058 (6)	−0.0006 (7)
C9	0.0199 (8)	0.0253 (9)	0.0192 (8)	−0.0021 (7)	0.0047 (6)	0.0019 (7)
C10	0.0189 (9)	0.0487 (13)	0.0294 (10)	−0.0018 (8)	0.0018 (7)	0.0004 (9)
C11	0.0278 (10)	0.0273 (11)	0.0244 (9)	−0.0048 (7)	0.0045 (7)	−0.0039 (7)

Geometric parameters (Å, º) top

Br1—C9	1.9962 (17)	C6—H6	0.9500
S1—C1	1.7548 (17)	C7—H7A	0.9800
S1—C7	1.7954 (19)	C7—H7B	0.9800
O1—C8	1.217 (2)	C7—H7C	0.9800
C1—C6	1.386 (2)	C8—C9	1.533 (2)
C1—C2	1.404 (2)	C9—C10	1.514 (2)
C2—C3	1.375 (2)	C9—C11	1.520 (2)
C2—H2	0.9500	C10—H10A	0.9800
C3—C4	1.402 (2)	C10—H10B	0.9800
C3—H3	0.9500	C10—H10C	0.9800
C4—C5	1.395 (2)	C11—H11A	0.9800
C4—C8	1.494 (2)	C11—H11B	0.9800
C5—C6	1.387 (2)	C11—H11C	0.9800
C5—H5	0.9500

C1—S1—C7	103.15 (9)	H7A—C7—H7C	109.5
C6—C1—C2	118.63 (16)	H7B—C7—H7C	109.5
C6—C1—S1	124.05 (13)	O1—C8—C4	119.29 (16)
C2—C1—S1	117.32 (13)	O1—C8—C9	118.05 (16)
C3—C2—C1	120.47 (16)	C4—C8—C9	122.63 (14)
C3—C2—H2	119.8	C10—C9—C11	110.31 (15)
C1—C2—H2	119.8	C10—C9—C8	110.88 (14)
C2—C3—C4	121.25 (15)	C11—C9—C8	114.50 (15)
C2—C3—H3	119.4	C10—C9—Br1	106.31 (12)
C4—C3—H3	119.4	C11—C9—Br1	108.46 (12)
C5—C4—C3	117.90 (16)	C8—C9—Br1	105.95 (11)
C5—C4—C8	124.62 (16)	C9—C10—H10A	109.5
C3—C4—C8	117.45 (14)	C9—C10—H10B	109.5
C6—C5—C4	121.01 (16)	H10A—C10—H10B	109.5
C6—C5—H5	119.5	C9—C10—H10C	109.5
C4—C5—H5	119.5	H10A—C10—H10C	109.5
C1—C6—C5	120.74 (15)	H10B—C10—H10C	109.5
C1—C6—H6	119.6	C9—C11—H11A	109.5
C5—C6—H6	119.6	C9—C11—H11B	109.5
S1—C7—H7A	109.5	H11A—C11—H11B	109.5
S1—C7—H7B	109.5	C9—C11—H11C	109.5
H7A—C7—H7B	109.5	H11A—C11—H11C	109.5
S1—C7—H7C	109.5	H11B—C11—H11C	109.5

C7—S1—C1—C6	−0.14 (17)	C4—C5—C6—C1	−0.5 (3)
C7—S1—C1—C2	179.45 (13)	C5—C4—C8—O1	−166.18 (16)
C6—C1—C2—C3	−0.2 (3)	C3—C4—C8—O1	12.1 (2)
S1—C1—C2—C3	−179.84 (13)	C5—C4—C8—C9	15.8 (3)
C1—C2—C3—C4	−0.2 (3)	C3—C4—C8—C9	−165.99 (15)
C2—C3—C4—C5	0.2 (3)	O1—C8—C9—C10	−3.6 (2)
C2—C3—C4—C8	−178.13 (15)	C4—C8—C9—C10	174.51 (16)
C3—C4—C5—C6	0.1 (2)	O1—C8—C9—C11	−129.15 (17)
C8—C4—C5—C6	178.36 (16)	C4—C8—C9—C11	48.9 (2)
C2—C1—C6—C5	0.6 (3)	O1—C8—C9—Br1	111.37 (16)
S1—C1—C6—C5	−179.83 (13)	C4—C8—C9—Br1	−70.55 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.98	2.47	3.359 (2)	150
C5—H5···Br1	0.95	2.78	3.387 (2)	123

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃BrOS
M_r	273.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	153
a, b, c (Å)	11.061 (3), 7.120 (2), 14.721 (4)
β (°)	97.638 (3)
V (Å³)	1149.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.73
Crystal size (mm)	0.27 × 0.23 × 0.18

Data collection
Diffractometer	Rigaku AFC10/Saturn724+ diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.433, 0.551
No. of measured, independent and observed [I > 2σ(I)] reflections	9900, 3625, 2901
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.073, 1.00
No. of reflections	3625
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.72

Computer programs: CrystalClear (Rigaku/MSC, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.98	2.47	3.359 (2)	150
C5—H5···Br1	0.95	2.78	3.387 (2)	123

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

References

Anuradha, N., Thiruvalluvar, A., Mahalinga, M. & Butcher, R. J. (2008). Acta Cryst. E64, o2118–o2119. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
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Rigaku/MSC. (2008). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
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Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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doi:10.1107/S1600536812021472

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