Dimeth­yl(2-oxo-2-phenyl­eth­yl)sulfanium bromide

Cao, Z.; Liu, W.; Yin, F.

doi:10.1107/S1600536810046404

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3197

https://doi.org/10.1107/S1600536810046404

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Dimethyl(2-oxo-2-phenylethyl)sulfanium bromide

Zhiling Cao,^a ^* Weiwei Liu ^a and Fujun Yin ^b

^aSchool of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005, People's Republic of China, and ^bJiangsu Marine Resources Development Research Institute, Lianyungang 222005, People's Republic of China
^*Correspondence e-mail: zhilingcao@yahoo.com.cn

(Received 26 October 2010; accepted 10 November 2010; online 17 November 2010)

Single crystals of the title compound, C₁₀H₁₃OS⁺·Br⁻, were obtained from ethyl acetate/ethyl ether after reaction of acetophenone with hydrobromic acid and dimethylsulfoxide. The carbonyl group is almost coplanar with the neighbouring phenyl ring [O—C—C—C = 178.9 (2)°]. The sulfanium group shows a trigonal–pyramidal geometry at the S atom. The crystal structure is stabilized by C—H⋯Br hydrogen-bonding interactions. Weak π–π interactions link adjacent phenyl rings [centroid–centroid distance = 3.946 (2) Å].

Related literature

For applications of phenacyl sulfanium salts in organic synthesis, see: Crivello et al. (2000 ); Hirano et al. (2001 ). For related structures, see: Dossena et al. (1983 ); Svensson et al. (1996 ).

Experimental

Crystal data

C₁₀H₁₃OS⁺·Br⁻
M_r = 261.17
Orthorhombic, P b c a
a = 15.7951 (17) Å
b = 7.4122 (8) Å
c = 19.007 (2) Å
V = 2225.3 (4) Å³
Z = 8
Mo Kα radiation
μ = 3.84 mm⁻¹
T = 296 K
0.40 × 0.38 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.309, T_max = 0.447
16148 measured reflections
2294 independent reflections
1840 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.070
S = 1.04
2294 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Br1ⁱ	0.93	2.92	3.844 (2)	171
C9—H9C⋯Br1ⁱⁱ	0.96	2.89	3.689 (2)	142
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046404/fb2228sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046404/fb2228Isup2.hkl

checkCIF report

Comment top

sulphanium salts, characterized by a low sulphur valence and relatively unstable carbon-sulphur bonds, have found a broad practical application in organic chemistry. For example, dimethylphenacylsulphanium salts have been used for synthesis of a new class of photoinitiators for cationic polymerization (Crivello et al., 2000) as well as of novel fluorophores (Hirano et al., 2001). In the crystal structure of the title complex (Fig. 1), the phenyl ring is coplanar with the carbonyl group. The sulphanium group shows a trigonal-pyramidal geometry. All the bond lengths and bond angles are within the normal range (Dossena et al., 1983; Svensson et al., 1996).

There are C—H···Br hydrogen-bond interactions that stabilize the crystal structure (Tab. 1, Fig. 2). Weak π-electron ring - π-electron ring interactions between the phenyl rings that are stacked along the b axis [the centroid-centroid distance equals to 3.946 (2) Å] are also present in the structure. The symmetry codes for each of the adjacent rings: 1/2-x,-1/2+y,z; 1/2-x,1/2+y,z.

Related literature top

For applications of phenacyl sulfanium salts in organic synthesis, see: Crivello et al. (2000); Hirano et al. (2001). For related structures, see: Dossena et al. (1983); Svensson et al. (1996).

Experimental top

Acetophenone (0.05 mol) was dissolved in a mixture of 48% (w%) aqueous hydrobromic acid (20 ml) and dimethylsulfoxide (40 ml). This solution was heated under reflux for 5 h to afford the title compound. The mixture was extracted three times, each time with 25 ml of ethyl acetate. Ethyl ether (15 ml) was added to the combined organic extracts. The solution was allowed to stand overnight. After filtration and washing with ethyl ether, colourless needle-shaped crystals were obtained. The crystals were as long as 13 mm being thick of about 0.4 mm.

Structure description top

For applications of phenacyl sulfanium salts in organic synthesis, see: Crivello et al. (2000); Hirano et al. (2001). For related structures, see: Dossena et al. (1983); Svensson et al. (1996).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal structure of the title compound, viewed along the b axis.

Dimethyl(2-oxo-2-phenylethyl)sulfanium bromide top

Crystal data top

C₁₀H₁₃OS⁺·Br⁻	D_x = 1.559 Mg m⁻³
M_r = 261.17	Melting point: 531 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5457 reflections
a = 15.7951 (17) Å	θ = 2.5–26.9°
b = 7.4122 (8) Å	µ = 3.84 mm⁻¹
c = 19.007 (2) Å	T = 296 K
V = 2225.3 (4) Å³	Plate, colourless
Z = 8	0.40 × 0.38 × 0.25 mm
F(000) = 1056

Data collection top

Bruker APEXII CCD diffractometer	2294 independent reflections
Radiation source: fine-focus sealed tube	1840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→19
T_min = 0.309, T_max = 0.447	k = −9→9
16148 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0328P)² + 1.2316P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2294 reflections	Δρ_max = 0.47 e Å⁻³
121 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
50 constraints	Extinction coefficient: 0.0092 (5)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₀H₁₃OS⁺·Br⁻	V = 2225.3 (4) Å³
M_r = 261.17	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.7951 (17) Å	µ = 3.84 mm⁻¹
b = 7.4122 (8) Å	T = 296 K
c = 19.007 (2) Å	0.40 × 0.38 × 0.25 mm

Data collection top

Bruker APEXII CCD diffractometer	2294 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1840 reflections with I > 2σ(I)
T_min = 0.309, T_max = 0.447	R_int = 0.034
16148 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.04	Δρ_max = 0.47 e Å⁻³
2294 reflections	Δρ_min = −0.40 e Å⁻³
121 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.143976 (16)	0.50139 (3)	0.223269 (13)	0.04541 (12)
O1	0.07571 (10)	0.1820 (3)	0.03073 (8)	0.0522 (5)
S1	0.06002 (3)	0.08052 (8)	0.17220 (3)	0.03120 (15)
C1	0.15917 (13)	0.0825 (3)	0.12611 (11)	0.0335 (5)
H1A	0.1988	0.1608	0.1504	0.040*
H1B	0.1828	−0.0383	0.1254	0.040*
C2	0.14674 (13)	0.1486 (3)	0.05159 (11)	0.0338 (5)
C3	0.22286 (13)	0.1698 (3)	0.00714 (11)	0.0331 (5)
C4	0.30359 (14)	0.1336 (3)	0.03261 (12)	0.0392 (5)
H4	0.3108	0.0926	0.0785	0.047*
C5	0.37317 (15)	0.1589 (4)	−0.01063 (14)	0.0507 (7)
H5	0.4273	0.1349	0.0062	0.061*
C6	0.36212 (17)	0.2195 (4)	−0.07849 (15)	0.0568 (8)
H6	0.4091	0.2377	−0.1071	0.068*
C7	0.28266 (18)	0.2535 (4)	−0.10436 (14)	0.0553 (7)
H7	0.2758	0.2924	−0.1505	0.066*
C8	0.21302 (16)	0.2300 (3)	−0.06179 (12)	0.0447 (6)
H8	0.1592	0.2543	−0.0791	0.054*
C9	0.01019 (16)	−0.1180 (3)	0.13854 (12)	0.0437 (6)
H9A	0.0471	−0.2196	0.1449	0.066*
H9B	−0.0014	−0.1024	0.0893	0.066*
H9C	−0.0419	−0.1388	0.1633	0.066*
C10	0.09574 (16)	0.0056 (3)	0.25659 (12)	0.0411 (6)
H10A	0.1271	−0.1045	0.2513	0.062*
H10B	0.0478	−0.0151	0.2866	0.062*
H10C	0.1314	0.0962	0.2772	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04414 (17)	0.04672 (18)	0.04538 (17)	−0.00352 (11)	0.00865 (10)	−0.00266 (11)
O1	0.0314 (9)	0.0831 (13)	0.0423 (9)	0.0042 (9)	−0.0031 (7)	0.0146 (9)
S1	0.0270 (3)	0.0370 (3)	0.0295 (3)	0.0031 (2)	0.0022 (2)	−0.0003 (2)
C1	0.0234 (10)	0.0458 (13)	0.0313 (11)	0.0017 (10)	0.0013 (8)	−0.0004 (10)
C2	0.0309 (12)	0.0390 (12)	0.0315 (11)	−0.0021 (9)	−0.0010 (9)	−0.0005 (10)
C3	0.0344 (11)	0.0347 (12)	0.0301 (10)	−0.0071 (10)	0.0032 (9)	−0.0041 (9)
C4	0.0342 (12)	0.0477 (14)	0.0358 (12)	−0.0047 (10)	0.0036 (9)	−0.0060 (10)
C5	0.0334 (13)	0.0658 (18)	0.0528 (15)	−0.0105 (12)	0.0081 (11)	−0.0180 (13)
C6	0.0515 (16)	0.0684 (19)	0.0506 (15)	−0.0242 (14)	0.0231 (12)	−0.0159 (14)
C7	0.0677 (18)	0.0636 (18)	0.0345 (12)	−0.0147 (15)	0.0112 (12)	0.0022 (12)
C8	0.0470 (14)	0.0511 (15)	0.0360 (12)	−0.0070 (12)	0.0014 (11)	0.0009 (11)
C9	0.0435 (13)	0.0475 (15)	0.0402 (13)	−0.0119 (11)	0.0050 (10)	−0.0053 (10)
C10	0.0441 (14)	0.0513 (15)	0.0278 (11)	0.0054 (11)	−0.0001 (10)	0.0027 (10)

Geometric parameters (Å, º) top

O1—C2	1.215 (3)	C5—H5	0.9300
S1—C9	1.788 (2)	C6—C7	1.371 (4)
S1—C10	1.789 (2)	C6—H6	0.9300
S1—C1	1.794 (2)	C7—C8	1.377 (4)
C1—C2	1.511 (3)	C7—H7	0.9300
C1—H1A	0.9700	C8—H8	0.9300
C1—H1B	0.9700	C9—H9A	0.9600
C2—C3	1.478 (3)	C9—H9B	0.9600
C3—C4	1.390 (3)	C9—H9C	0.9600
C3—C8	1.393 (3)	C10—H10A	0.9600
C4—C5	1.385 (3)	C10—H10B	0.9600
C4—H4	0.9300	C10—H10C	0.9600
C5—C6	1.377 (4)

C9—S1—C10	101.78 (12)	C7—C6—C5	120.8 (2)
C9—S1—C1	102.49 (11)	C7—C6—H6	119.6
C10—S1—C1	99.50 (11)	C5—C6—H6	119.6
C2—C1—S1	110.29 (15)	C6—C7—C8	119.8 (2)
C2—C1—H1A	109.6	C6—C7—H7	120.1
S1—C1—H1A	109.6	C8—C7—H7	120.1
C2—C1—H1B	109.6	C7—C8—C3	120.3 (2)
S1—C1—H1B	109.6	C7—C8—H8	119.9
H1A—C1—H1B	108.1	C3—C8—H8	119.9
O1—C2—C3	122.9 (2)	S1—C9—H9A	109.5
O1—C2—C1	119.45 (19)	S1—C9—H9B	109.5
C3—C2—C1	117.68 (18)	H9A—C9—H9B	109.5
C4—C3—C8	119.5 (2)	S1—C9—H9C	109.5
C4—C3—C2	121.77 (19)	H9A—C9—H9C	109.5
C8—C3—C2	118.8 (2)	H9B—C9—H9C	109.5
C5—C4—C3	119.7 (2)	S1—C10—H10A	109.5
C5—C4—H4	120.2	S1—C10—H10B	109.5
C3—C4—H4	120.2	H10A—C10—H10B	109.5
C6—C5—C4	120.0 (2)	S1—C10—H10C	109.5
C6—C5—H5	120.0	H10A—C10—H10C	109.5
C4—C5—H5	120.0	H10B—C10—H10C	109.5

C9—S1—C1—C2	77.33 (19)	C8—C3—C4—C5	0.4 (3)
C10—S1—C1—C2	−178.25 (17)	C2—C3—C4—C5	−178.7 (2)
S1—C1—C2—O1	−3.6 (3)	C3—C4—C5—C6	0.0 (4)
S1—C1—C2—C3	176.26 (17)	C4—C5—C6—C7	−0.8 (4)
O1—C2—C3—C4	178.9 (2)	C5—C6—C7—C8	1.2 (4)
C1—C2—C3—C4	−1.0 (3)	C6—C7—C8—C3	−0.7 (4)
O1—C2—C3—C8	−0.3 (4)	C4—C3—C8—C7	−0.1 (4)
C1—C2—C3—C8	179.8 (2)	C2—C3—C8—C7	179.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Br1ⁱ	0.93	2.92	3.844 (2)	171
C9—H9C···Br1ⁱⁱ	0.96	2.89	3.689 (2)	142

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃OS⁺·Br⁻
M_r	261.17
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	15.7951 (17), 7.4122 (8), 19.007 (2)
V (Å³)	2225.3 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.84
Crystal size (mm)	0.40 × 0.38 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.309, 0.447
No. of measured, independent and observed [I > 2σ(I)] reflections	16148, 2294, 1840
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.04
No. of reflections	2294
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.40

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2010), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Br1ⁱ	0.93	2.92	3.844 (2)	171.1
C9—H9C···Br1ⁱⁱ	0.96	2.89	3.689 (2)	142.0

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Jiangsu Education Department (grant No. 10 K J A170003) and Huaihai Institute of Technology (grant No. KX10016) for financial support.

References

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