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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 3| March 2012| Page o637
doi:10.1107/S1600536812002899

1-Ethenyl-4-[(phenylsulfanyl)methyl]­benzene

Alcives Avila-Sorrosa,a Reyna Reyes-Martínez,a* Simón Hernández-Ortegaa and David Morales-Moralesa

aInstituto de Química, Universidad Nacional Autónoma de México, Circuito exterior, Ciudad Universitaria, México DF 04510, Mexico
*Correspondence e-mail: rrm@uaem.mx

(Received 20 January 2012; accepted 23 January 2012; online 10 February 2012)

The dihedral angle between the aromatic rings in the title compound, C15H14S, is 72.38 (7)°. In the crystal, the mol­ecules are connected by C—H⋯π inter­actions.

Related literature

For aryl­sulfides used as ligands in coordination chemistry, see: Olivos-Suárez et al. (2007[Olivos-Suárez, A. I., Ríos-Moreno, G., Hernández-Ortega, S., Toscano, R. A., García, J. J. & Morales-Morales, D. (2007). Inorg. Chim. Acta, 360, 4133-4141.]); Fierro-Arias et al. (2005[Fierro-Arias, J. G., Redón, R., García, J.-J., Hernández-Ortega, S., Toscano, R. A. & Morales-Morales, D. (2005). J. Mol. Catal. A Chem. 233, 17-27.]).

[Scheme 1]

Experimental

Crystal data

  • C15H14S

  • Mr = 226.32

  • Monoclinic, P 21 /c

  • a = 8.3042 (19) Å

  • b = 14.642 (3) Å

  • c = 10.370 (2) Å

  • β = 92.912 (4)°

  • V = 1259.3 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.23 mm−1

  • T = 298 K

  • 0.36 × 0.19 × 0.10 mm
Data collection

  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.936, Tmax = 0.982

  • 10072 measured reflections

  • 2314 independent reflections

  • 1525 reflections with I > 2σ(I)

  • Rint = 0.034
Refinement

  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.140

  • S = 1.03

  • 2314 reflections

  • 145 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.27 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Inter­molecular C—H⋯π inter­actions in the title compound (Å)

H atom Centroid Distance Symmetry code
H9 C1–C6 2.746 (−x + 1, −y + 1, −z)
H12 C1–C6 2.873 (−x, y + [{1\over 2}], −z + [{1\over 2}])

Data collection: SMART (Bruker, 2007[Bruker (2007). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SAINT (Bruker, 2007[Bruker (2007). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812002899/bt5794sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002899/bt5794Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812002899/bt5794Isup3.cml

checkCIF report


Comment top

Organosulfur compounds are important in synthetic organic chemistry, their applications include protecting groups (thioacetals), reversing of the polarity (Umpolong), in enhancement of the acidity of C—H bonds, as well as in transfer of chirality from sulfur to carbon, among many other. Additionally, sulfur-containing groups are frequently found in important drugs used in the treatment of various diseases like diabetes, Alzheimer's, Parkinson's, cancer, and HIV. Thus, given their potential applications of these species, the synthesis of these compounds including catalytic procedures for their efficient production, has become an area of growing interest, this being particularly true for the attaining of non-symmetric sulfides. Moreover, recently arylsulfides have been used successfully as ligands in coordination chemistry (Olivos-Suárez et al., 2007) where simple variations of the substitution at the sulfur makes them a very interesting set of ligands for the fine tuning of electron-donor properties and thus modulating the metal reactivity (Fierro-Arias et al., 2005).

The molecular structure of the title compound is showed in Fig. 1. The bond distances and angles are within normal values. The geometry of the molecule exhibits non-coplanarity of the phenyl rings, with a dihedral angle of 72.38 (7)°. The molecules are stabilized in the solid state by weak C—H-π Cg(C1—C6) intermolecular interactions, [C9—H9B—Cg 2.746 Å, C9—Cg 3.488 Å, C9—H9—Cg 132.9°, symm. code -x + 1, -y + 1, -z, C12—H12—Cg 2.873 Å, C12—Cg 3.651 Å, C12—H12—Cg, 141.9° symm operator 2]. The C—H-π interaction between the methylene group and the aromatic ring Cg of the molecules generates a dimeric motif which are extended by C—H-π interaction between C12—H12–Cg generating a two-dimensional sheet structure (Fig. 2).

Related literature top

For arylsulfides used as ligands in coordination chemistry, see: Olivos-Suárez et al. (2007); Fierro-Arias et al. (2005).

Experimental top

To a suspension of NaH (126 mg, 5.5 mmol) in 20 ml of THF, benzenethiol was added dropwise (0.34 ml, 5 mmol). The resulting suspension was stirred for 10 min and after this time chloromethyl-vinyl-benzene (this starting material was used as a mixture 60:40% of 1-chloromethyl-3-vinyl-benzene and 1-chloromethyl-4-vinyl-benzene as supplied by Aldrich Chemical Co., 0.7 ml, 760 mg, 5 mmol) was added. The reaction mixture was then allowed to proceed under stirring for further 3 h. Upon completion the reaction mixture was extracted with CH2Cl2 (4 × 20 ml) and the combined organic fractions were washed with H2O (2 × 50 ml) and dried with Na2SO4, filtered and evaporated under vacuum to afford 1.10 g (4.84 mmol, 97%) of a white solid consisting in a mixture of a 1-phenylsulfanylmethyl-3-vinyl-benzene and 1-phenylsulfanylmethyl-4-vinyl-benzene (60:40 ca). Crystals suitable for X-ray analysis were obtained from a slow evaporation of a saturated solution of this mixture in CH2Cl2. IR (KBr): 3087, 3003, 2921, 2848, 1588, 1509, 1488, 1091, 993, 907, 851, 820, 627 cm-1. EM–IE: 226 (40, [M+]), 117 (100), 115 (30) / 226 (15, [M+]), 117 (100), 115 (20) m/z (%). 1H NMR (300 MHz, CDCl3), d (p.p.m.): 7.37–7.17 (m, 18H) 6.73 (dd, 1H), 6.68 (dd, 1H), 5.74 (dd, 2H), 5.26 (dd, 2H), 4.12 (s, 2H), 4.13 (s, 2H).

Refinement top

H atoms were included in calculated positions (C—H = 0.93 Å), and refined using a riding model with Uiso(H) = 1.2Ueq of the carrier atom.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Crystal structure of the title compound with the numbering scheme. Displacement ellipsoids are shown at the 30% probability. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. C—H—π dimeric motif, by C9—H9B—Cg and two-dimensional sheet structure formed through C—H—π interactions, C12—H12—Cg.
1-Ethenyl-4-[(phenylsulfanyl)methyl]benzene top
Crystal data top
C15H14SF(000) = 480
Mr = 226.32Dx = 1.194 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2634 reflections
a = 8.3042 (19) Åθ = 2.4–24.2°
b = 14.642 (3) ŵ = 0.23 mm−1
c = 10.370 (2) ÅT = 298 K
β = 92.912 (4)°Block, colourless
V = 1259.3 (5) Å30.36 × 0.19 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		2314 independent reflections
Radiation source: fine-focus sealed tube1525 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 0.661 pixels mm-1θmax = 25.4°, θmin = 2.4°
ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		k = −17→17
Tmin = 0.936, Tmax = 0.982l = −12→12
10072 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0603P)2 + 0.2262P]
where P = (Fo2 + 2Fc2)/3
2314 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.27 e Å−3
1 restraintΔρmin = −0.13 e Å−3
Crystal data top
C15H14SV = 1259.3 (5) Å3
Mr = 226.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3042 (19) ŵ = 0.23 mm−1
b = 14.642 (3) ÅT = 298 K
c = 10.370 (2) Å0.36 × 0.19 × 0.10 mm
β = 92.912 (4)°
Data collection top
Bruker SMART APEX CCD
diffractometer		2314 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		1525 reflections with I > 2σ(I)
Tmin = 0.936, Tmax = 0.982Rint = 0.034
10072 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0571 restraint
wR(F2) = 0.140H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å−3
2314 reflectionsΔρmin = −0.13 e Å−3
145 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
xyzUiso*/Ueq
S10.16819 (9)0.60414 (5)0.19138 (7)0.0904 (3)
C10.3712 (4)0.2798 (2)0.0931 (3)0.0885 (8)
C20.2757 (4)0.3174 (2)−0.0058 (3)0.0930 (9)
H20.22630.2793−0.06760.112*
C30.2521 (3)0.4107 (2)−0.0150 (3)0.0885 (8)
H30.18670.4343−0.08240.106*
C40.3246 (3)0.4690 (2)0.0748 (3)0.0757 (7)
C50.4190 (4)0.4312 (2)0.1723 (3)0.0886 (8)
H50.46850.46910.23430.106*
C60.4426 (4)0.3392 (3)0.1813 (3)0.0974 (9)
H60.50870.31610.24860.117*
C70.4016 (5)0.1808 (3)0.1094 (4)0.1230 (12)
H70.47420.16400.17650.148*
C80.3390 (6)0.1155 (3)0.0413 (5)0.1552 (17)
H8A0.26560.1284−0.02700.186*
H8B0.36700.05530.06030.186*
C90.2985 (3)0.5699 (2)0.0659 (3)0.0873 (8)
H9A0.24930.5855−0.01800.105*
H9B0.40090.60150.07640.105*
C100.1452 (3)0.7229 (2)0.1694 (2)0.0752 (7)
C110.0489 (3)0.7681 (2)0.2549 (3)0.0869 (8)
H110.00090.73540.31950.104*
C120.0245 (4)0.8600 (2)0.2446 (3)0.0995 (10)
H12−0.04040.88910.30240.119*
C130.0937 (4)0.9101 (2)0.1508 (3)0.1001 (9)
H130.07640.97270.14460.120*
C140.1886 (4)0.8663 (2)0.0666 (3)0.0981 (9)
H140.23630.89970.00250.118*
C150.2150 (3)0.7736 (2)0.0749 (3)0.0860 (8)
H150.28010.74500.01660.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0786 (5)0.0978 (6)0.0979 (6)0.0027 (4)0.0353 (4)0.0027 (4)
C10.0791 (19)0.089 (2)0.100 (2)0.0046 (16)0.0288 (17)0.0090 (19)
C20.0802 (19)0.102 (2)0.098 (2)−0.0160 (17)0.0154 (17)−0.0222 (19)
C30.0724 (17)0.109 (2)0.0849 (19)0.0017 (16)0.0074 (15)−0.0013 (18)
C40.0635 (15)0.0884 (19)0.0771 (17)−0.0015 (14)0.0203 (13)−0.0026 (16)
C50.0860 (19)0.100 (2)0.0804 (19)−0.0012 (17)0.0075 (16)−0.0066 (17)
C60.091 (2)0.113 (3)0.089 (2)0.0079 (19)0.0086 (17)0.005 (2)
C70.122 (3)0.122 (3)0.129 (3)−0.006 (2)0.034 (2)−0.002 (3)
C80.161 (4)0.125 (4)0.183 (5)−0.010 (3)0.039 (4)0.005 (3)
C90.0807 (18)0.098 (2)0.0854 (18)0.0025 (15)0.0248 (14)−0.0026 (16)
C100.0550 (13)0.0940 (19)0.0771 (16)−0.0007 (13)0.0100 (12)−0.0057 (14)
C110.0699 (16)0.104 (2)0.0886 (19)0.0054 (15)0.0247 (14)−0.0012 (16)
C120.088 (2)0.114 (3)0.098 (2)0.0153 (19)0.0257 (18)−0.014 (2)
C130.101 (2)0.095 (2)0.105 (2)0.0097 (18)0.0141 (19)−0.0066 (19)
C140.108 (2)0.096 (2)0.093 (2)−0.0036 (18)0.0259 (18)0.0007 (18)
C150.0818 (18)0.095 (2)0.0832 (18)−0.0009 (15)0.0231 (15)−0.0068 (16)
Geometric parameters (Å, º) top
S1—C101.763 (3)C8—H8A0.9300
S1—C91.805 (3)C8—H8B0.9300
C1—C61.374 (4)C9—H9A0.9700
C1—C21.379 (4)C9—H9B0.9700
C1—C71.481 (5)C10—C151.380 (4)
C2—C31.382 (4)C10—C111.390 (3)
C2—H20.9300C11—C121.364 (4)
C3—C41.379 (4)C11—H110.9300
C3—H30.9300C12—C131.368 (4)
C4—C51.365 (4)C12—H120.9300
C4—C91.495 (4)C13—C141.366 (4)
C5—C61.363 (4)C13—H130.9300
C5—H50.9300C14—C151.377 (4)
C6—H60.9300C14—H140.9300
C7—C81.282 (4)C15—H150.9300
C7—H70.9300
C10—S1—C9104.23 (13)C4—C9—S1108.70 (19)
C6—C1—C2117.0 (3)C4—C9—H9A110.0
C6—C1—C7118.6 (3)S1—C9—H9A110.0
C2—C1—C7124.4 (4)C4—C9—H9B110.0
C1—C2—C3121.3 (3)S1—C9—H9B110.0
C1—C2—H2119.3H9A—C9—H9B108.3
C3—C2—H2119.3C15—C10—C11118.2 (3)
C4—C3—C2120.6 (3)C15—C10—S1125.1 (2)
C4—C3—H3119.7C11—C10—S1116.6 (2)
C2—C3—H3119.7C12—C11—C10120.5 (3)
C5—C4—C3117.6 (3)C12—C11—H11119.8
C5—C4—C9121.5 (3)C10—C11—H11119.8
C3—C4—C9120.9 (3)C11—C12—C13121.2 (3)
C6—C5—C4121.8 (3)C11—C12—H12119.4
C6—C5—H5119.1C13—C12—H12119.4
C4—C5—H5119.1C14—C13—C12118.7 (3)
C5—C6—C1121.6 (3)C14—C13—H13120.7
C5—C6—H6119.2C12—C13—H13120.7
C1—C6—H6119.2C13—C14—C15121.2 (3)
C8—C7—C1127.2 (5)C13—C14—H14119.4
C8—C7—H7116.4C15—C14—H14119.4
C1—C7—H7116.4C14—C15—C10120.2 (3)
C7—C8—H8A120.0C14—C15—H15119.9
C7—C8—H8B120.0C10—C15—H15119.9
H8A—C8—H8B120.0
C6—C1—C2—C3−0.6 (4)C3—C4—C9—S1107.0 (3)
C7—C1—C2—C3179.8 (3)C10—S1—C9—C4−179.3 (2)
C1—C2—C3—C40.4 (4)C9—S1—C10—C150.1 (3)
C2—C3—C4—C5−0.3 (4)C9—S1—C10—C11−179.8 (2)
C2—C3—C4—C9−179.5 (2)C15—C10—C11—C120.2 (4)
C3—C4—C5—C60.4 (4)S1—C10—C11—C12−179.9 (2)
C9—C4—C5—C6179.7 (3)C10—C11—C12—C13−0.1 (5)
C4—C5—C6—C1−0.7 (4)C11—C12—C13—C140.0 (5)
C2—C1—C6—C50.7 (4)C12—C13—C14—C150.0 (5)
C7—C1—C6—C5−179.6 (3)C13—C14—C15—C100.0 (5)
C6—C1—C7—C8176.0 (4)C11—C10—C15—C14−0.1 (4)
C2—C1—C7—C8−4.4 (6)S1—C10—C15—C14180.0 (2)
C5—C4—C9—S1−72.3 (3)

Experimental details

Crystal data
Chemical formulaC15H14S
Mr226.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)8.3042 (19), 14.642 (3), 10.370 (2)
β (°) 92.912 (4)
V (Å3)1259.3 (5)
Z4
Radiation typeMo Kα
µ (mm−1)0.23
Crystal size (mm)0.36 × 0.19 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.936, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections		10072, 2314, 1525
Rint0.034
(sin θ/λ)max (Å−1)0.604
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.140, 1.03
No. of reflections2314
No. of parameters145
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.27, −0.13

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Intermolecular C—H···π interactions in the title compound (Å) top
H atomCentroidDistanceSymmetry code
H9C1–C62.746(-x+1, -y+1, -z)
H12C1–C62.873(-x, y+1/2, -z+1/2)
 

Acknowledgements

RRM thanks CONACYT for a postdoctoral scholarship (Agreement No. 290586-UNAM). Support of this research was provided by CONACYT (grant No. 154732) and PAPIIT (grant No. IN201711). DMM acknowledges Dr Ruben A. Toscano for technical assistance.

References

First citationBruker (2007). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFierro-Arias, J. G., Redón, R., García, J.-J., Hernández-Ortega, S., Toscano, R. A. & Morales-Morales, D. (2005). J. Mol. Catal. A Chem. 233, 17–27.  CAS Google Scholar
 First citationOlivos-Suárez, A. I., Ríos-Moreno, G., Hernández-Ortega, S., Toscano, R. A., García, J. J. & Morales-Morales, D. (2007). Inorg. Chim. Acta, 360, 4133–4141.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 3| March 2012| Page o637
doi:10.1107/S1600536812002899
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