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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3197.
Published online 2010 November 17. doi:  10.1107/S1600536810046404
PMCID: PMC3011718

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

Abstract

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 [triangle]); Hirano et al. (2001 [triangle]). For related structures, see: Dossena et al. (1983 [triangle]); Svensson et al. (1996 [triangle]).

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Object name is e-66-o3197-scheme1.jpg

Experimental

Crystal data

  • C10H13OS+·Br
  • M r = 261.17
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3197-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.027
  • wR(F 2) = 0.070
  • S = 1.04
  • 2294 reflections
  • 121 parameters
  • H-atom parameters constrained
  • Δρmax = 0.47 e Å−3
  • Δρmin = −0.40 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046404/fb2228Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All the hydrogens could have been discerned in the difference electron map. However, the hydrogens were situated into the idealized postions and treated in the riding mode approximation. The used constraints were as follows: C—H = 0.93 (aryl C), C—H = 0.97 (methylene C), C—H = 0.96 Å (methyl C). Uiso(H) = 1.2Ueq(Caryl/Cmethylene), Uiso(H) = 1.5Ueq(Cmethyl).

Figures

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.

Crystal data

C10H13OS+·BrDx = 1.559 Mg m3
Mr = 261.17Melting point: 531 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5457 reflections
a = 15.7951 (17) Åθ = 2.5–26.9°
b = 7.4122 (8) ŵ = 3.84 mm1
c = 19.007 (2) ÅT = 296 K
V = 2225.3 (4) Å3Plate, colourless
Z = 80.40 × 0.38 × 0.25 mm
F(000) = 1056

Data collection

Bruker APEXII CCD diffractometer2294 independent reflections
Radiation source: fine-focus sealed tube1840 reflections with I > 2σ(I)
graphiteRint = 0.034
[var phi] and ω scansθmax = 26.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −18→19
Tmin = 0.309, Tmax = 0.447k = −9→9
16148 measured reflectionsl = −23→23

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.070w = 1/[σ2(Fo2) + (0.0328P)2 + 1.2316P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2294 reflectionsΔρmax = 0.47 e Å3
121 parametersΔρmin = −0.39 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
50 constraintsExtinction coefficient: 0.0092 (5)
Primary atom site location: structure-invariant direct methods

Special details

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)

xyzUiso*/Ueq
Br10.143976 (16)0.50139 (3)0.223269 (13)0.04541 (12)
O10.07571 (10)0.1820 (3)0.03073 (8)0.0522 (5)
S10.06002 (3)0.08052 (8)0.17220 (3)0.03120 (15)
C10.15917 (13)0.0825 (3)0.12611 (11)0.0335 (5)
H1A0.19880.16080.15040.040*
H1B0.1828−0.03830.12540.040*
C20.14674 (13)0.1486 (3)0.05159 (11)0.0338 (5)
C30.22286 (13)0.1698 (3)0.00714 (11)0.0331 (5)
C40.30359 (14)0.1336 (3)0.03261 (12)0.0392 (5)
H40.31080.09260.07850.047*
C50.37317 (15)0.1589 (4)−0.01063 (14)0.0507 (7)
H50.42730.13490.00620.061*
C60.36212 (17)0.2195 (4)−0.07849 (15)0.0568 (8)
H60.40910.2377−0.10710.068*
C70.28266 (18)0.2535 (4)−0.10436 (14)0.0553 (7)
H70.27580.2924−0.15050.066*
C80.21302 (16)0.2300 (3)−0.06179 (12)0.0447 (6)
H80.15920.2543−0.07910.054*
C90.01019 (16)−0.1180 (3)0.13854 (12)0.0437 (6)
H9A0.0471−0.21960.14490.066*
H9B−0.0014−0.10240.08930.066*
H9C−0.0419−0.13880.16330.066*
C100.09574 (16)0.0056 (3)0.25659 (12)0.0411 (6)
H10A0.1271−0.10450.25130.062*
H10B0.0478−0.01510.28660.062*
H10C0.13140.09620.27720.062*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.04414 (17)0.04672 (18)0.04538 (17)−0.00352 (11)0.00865 (10)−0.00266 (11)
O10.0314 (9)0.0831 (13)0.0423 (9)0.0042 (9)−0.0031 (7)0.0146 (9)
S10.0270 (3)0.0370 (3)0.0295 (3)0.0031 (2)0.0022 (2)−0.0003 (2)
C10.0234 (10)0.0458 (13)0.0313 (11)0.0017 (10)0.0013 (8)−0.0004 (10)
C20.0309 (12)0.0390 (12)0.0315 (11)−0.0021 (9)−0.0010 (9)−0.0005 (10)
C30.0344 (11)0.0347 (12)0.0301 (10)−0.0071 (10)0.0032 (9)−0.0041 (9)
C40.0342 (12)0.0477 (14)0.0358 (12)−0.0047 (10)0.0036 (9)−0.0060 (10)
C50.0334 (13)0.0658 (18)0.0528 (15)−0.0105 (12)0.0081 (11)−0.0180 (13)
C60.0515 (16)0.0684 (19)0.0506 (15)−0.0242 (14)0.0231 (12)−0.0159 (14)
C70.0677 (18)0.0636 (18)0.0345 (12)−0.0147 (15)0.0112 (12)0.0022 (12)
C80.0470 (14)0.0511 (15)0.0360 (12)−0.0070 (12)0.0014 (11)0.0009 (11)
C90.0435 (13)0.0475 (15)0.0402 (13)−0.0119 (11)0.0050 (10)−0.0053 (10)
C100.0441 (14)0.0513 (15)0.0278 (11)0.0054 (11)−0.0001 (10)0.0027 (10)

Geometric parameters (Å, °)

O1—C21.215 (3)C5—H50.9300
S1—C91.788 (2)C6—C71.371 (4)
S1—C101.789 (2)C6—H60.9300
S1—C11.794 (2)C7—C81.377 (4)
C1—C21.511 (3)C7—H70.9300
C1—H1A0.9700C8—H80.9300
C1—H1B0.9700C9—H9A0.9600
C2—C31.478 (3)C9—H9B0.9600
C3—C41.390 (3)C9—H9C0.9600
C3—C81.393 (3)C10—H10A0.9600
C4—C51.385 (3)C10—H10B0.9600
C4—H40.9300C10—H10C0.9600
C5—C61.377 (4)
C9—S1—C10101.78 (12)C7—C6—C5120.8 (2)
C9—S1—C1102.49 (11)C7—C6—H6119.6
C10—S1—C199.50 (11)C5—C6—H6119.6
C2—C1—S1110.29 (15)C6—C7—C8119.8 (2)
C2—C1—H1A109.6C6—C7—H7120.1
S1—C1—H1A109.6C8—C7—H7120.1
C2—C1—H1B109.6C7—C8—C3120.3 (2)
S1—C1—H1B109.6C7—C8—H8119.9
H1A—C1—H1B108.1C3—C8—H8119.9
O1—C2—C3122.9 (2)S1—C9—H9A109.5
O1—C2—C1119.45 (19)S1—C9—H9B109.5
C3—C2—C1117.68 (18)H9A—C9—H9B109.5
C4—C3—C8119.5 (2)S1—C9—H9C109.5
C4—C3—C2121.77 (19)H9A—C9—H9C109.5
C8—C3—C2118.8 (2)H9B—C9—H9C109.5
C5—C4—C3119.7 (2)S1—C10—H10A109.5
C5—C4—H4120.2S1—C10—H10B109.5
C3—C4—H4120.2H10A—C10—H10B109.5
C6—C5—C4120.0 (2)S1—C10—H10C109.5
C6—C5—H5120.0H10A—C10—H10C109.5
C4—C5—H5120.0H10B—C10—H10C109.5
C9—S1—C1—C277.33 (19)C8—C3—C4—C50.4 (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—C60.0 (4)
S1—C1—C2—C3176.26 (17)C4—C5—C6—C7−0.8 (4)
O1—C2—C3—C4178.9 (2)C5—C6—C7—C81.2 (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—C8179.8 (2)C2—C3—C8—C7179.2 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4···Br1i0.932.923.844 (2)171
C9—H9C···Br1ii0.962.893.689 (2)142

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2228).

References

  • Brandenburg, K. (2010). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Crivello, J. V. & Kong, S. (2000). Macromolecules, 33, 825–832.
  • Dossena, A., Marchelli, R., Armani, E., Gasparri, F. G. & Ferrari, B. M. (1983). J. Chem. Soc. Chem. Commun.21, 1196–1197.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Hirano, K., Minakata, S. & Komatsu, M. (2001). Bull. Chem. Soc. Jpn, 74, 1567–1575.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Svensson, P. H. & Kloo, L. (1996). Acta Cryst. C52, 2580–2581.
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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