organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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 ππ 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[Crivello, J. V. & Kong, S. (2000). Macromolecules, 33, 825-832.]); Hirano et al. (2001[Hirano, K., Minakata, S. & Komatsu, M. (2001). Bull. Chem. Soc. Jpn, 74, 1567-1575.]). For related structures, see: Dossena et al. (1983[Dossena, A., Marchelli, R., Armani, E., Gasparri, F. G. & Ferrari, B. M. (1983). J. Chem. Soc. Chem. Commun. 21, 1196-1197.]); Svensson et al. (1996[Svensson, P. H. & Kloo, L. (1996). Acta Cryst. C52, 2580-2581.]).

[Scheme 1]

Experimental

Crystal data
  • C10H13OS+·Br

  • Mr = 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.309, Tmax = 0.447

  • 16148 measured reflections

  • 2294 independent reflections

  • 1840 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

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).

Structure description 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.

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
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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+·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 top
Bruker APEXII CCD
diffractometer
2294 independent reflections
Radiation source: fine-focus sealed tube1840 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
φ and ω scansθmax = 26.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1819
Tmin = 0.309, Tmax = 0.447k = 99
16148 measured reflectionsl = 2323
Refinement top
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) = 0.070 w = 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 = 0.40 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
Crystal data top
C10H13OS+·BrV = 2225.3 (4) Å3
Mr = 261.17Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.7951 (17) ŵ = 3.84 mm1
b = 7.4122 (8) ÅT = 296 K
c = 19.007 (2) Å0.40 × 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)
Tmin = 0.309, Tmax = 0.447Rint = 0.034
16148 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.070H-atom parameters constrained
S = 1.04Δρmax = 0.47 e Å3
2294 reflectionsΔρmin = 0.40 e Å3
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
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*
H1B0.18280.03830.12540.040*
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)
H60.40910.23770.10710.068*
C70.28266 (18)0.2535 (4)0.10436 (14)0.0553 (7)
H70.27580.29240.15050.066*
C80.21302 (16)0.2300 (3)0.06179 (12)0.0447 (6)
H80.15920.25430.07910.054*
C90.01019 (16)0.1180 (3)0.13854 (12)0.0437 (6)
H9A0.04710.21960.14490.066*
H9B0.00140.10240.08930.066*
H9C0.04190.13880.16330.066*
C100.09574 (16)0.0056 (3)0.25659 (12)0.0411 (6)
H10A0.12710.10450.25130.062*
H10B0.04780.01510.28660.062*
H10C0.13140.09620.27720.062*
Atomic displacement parameters (Å2) top
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, º) top
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—C2178.25 (17)C2—C3—C4—C5178.7 (2)
S1—C1—C2—O13.6 (3)C3—C4—C5—C60.0 (4)
S1—C1—C2—C3176.26 (17)C4—C5—C6—C70.8 (4)
O1—C2—C3—C4178.9 (2)C5—C6—C7—C81.2 (4)
C1—C2—C3—C41.0 (3)C6—C7—C8—C30.7 (4)
O1—C2—C3—C80.3 (4)C4—C3—C8—C70.1 (4)
C1—C2—C3—C8179.8 (2)C2—C3—C8—C7179.2 (2)
Hydrogen-bond geometry (Å, º) top
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, y1/2, z; (ii) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H13OS+·Br
Mr261.17
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)15.7951 (17), 7.4122 (8), 19.007 (2)
V3)2225.3 (4)
Z8
Radiation typeMo Kα
µ (mm1)3.84
Crystal size (mm)0.40 × 0.38 × 0.25
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.309, 0.447
No. of measured, independent and
observed [I > 2σ(I)] reflections
16148, 2294, 1840
Rint0.034
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.070, 1.04
No. of reflections2294
No. of parameters121
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C4—H4···Br1i0.932.923.844 (2)171.1
C9—H9C···Br1ii0.962.893.689 (2)142.0
Symmetry codes: (i) x+1/2, y1/2, z; (ii) x, y1/2, 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

First citationBrandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCrivello, J. V. & Kong, S. (2000). Macromolecules, 33, 825–832.  Web of Science CrossRef CAS Google Scholar
First citationDossena, A., Marchelli, R., Armani, E., Gasparri, F. G. & Ferrari, B. M. (1983). J. Chem. Soc. Chem. Commun. 21, 1196–1197.  CrossRef Web of Science Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationHirano, K., Minakata, S. & Komatsu, M. (2001). Bull. Chem. Soc. Jpn, 74, 1567–1575.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSvensson, P. H. & Kloo, L. (1996). Acta Cryst. C52, 2580–2581.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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