Bis(benzyl­sulfan­yl)methane

Yang, H.; Kim, T.H.; Moon, S.-H.; Kim, J.

doi:10.1107/S1600536810019641

organic compounds

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Volume 66| Part 6| June 2010| Page o1519

https://doi.org/10.1107/S1600536810019641

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Bis(benzylsulfanyl)methane

Hojin Yang,^a Tae Ho Kim,^a ^* Suk-Hee Moon ^b and Jineun Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea, and ^bSubdivision of Food Science, Kyungnam College of Information and Technology, Busan 616-701, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

(Received 14 May 2010; accepted 25 May 2010; online 29 May 2010)

In the title compound, C₁₅H₁₆S₂, the structure of the dithioalkyl chain is a helix with an all-cis conformation. The dihedral angle between the mean planes of the terminal aromatic rings is 74.60 (4)°. In the crystal structure, weak C—H⋯π interactions contribute to the stabilization of the packing.

Related literature

For the synthesis of the title ligand, see: Cohen et al. (1980 ). For related structures, see: Li et al. (2005 ); Tanaka & Ajiki (2005 ).

Experimental

Crystal data

C₁₅H₁₆S₂
M_r = 260.40
Monoclinic, P 2₁ /c
a = 5.5146 (1) Å
b = 12.2628 (3) Å
c = 20.0128 (5) Å
β = 101.156 (1)°
V = 1327.78 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 173 K
0.22 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.922, T_max = 0.946
12942 measured reflections
3335 independent reflections
2977 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.082
S = 1.04
3335 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯Cgⁱ	0.95	2.85	3.71	151
Symmetry code: (i) x, y-1, z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810019641/sj5008sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019641/sj5008Isup2.hkl

checkCIF report

Comment top

Dithio acetals (RSCH₂SR) have received considerable attention in the literature (Li et al., 2005; Tanaka & Ajiki, 2005). We report herein the crystal structure of the title compound. In asymmetric unit, the conformation of dithioalkyl chain is all cis and the dihedral angle between the aromatic rings is 74.60 (4)°. In the crystal structure (Fig. 1), the bond lengths and angles are within normal ranges.

A weak C13—H13···Cg = 2.85 Å interaction (Cg is the centroid of the C1···C6 ring) is observed, Table 1. Weak intermolecular S···S interactions with 3.4732 (6)Å also exist. These intermolecular interactions may be effective in the stabilization of the structure, Fig. 2.

Related literature top

For the synthesis of the ligand, see: Cohen et al. (1980). For related structures, see: Li et al. (2005); Tanaka & Ajiki (2005).

Experimental top

The title compound was synthesised according to the published procedure (Cohen et al., 1980) and recrystallized from petroleum ether.

Structure description top

For the synthesis of the ligand, see: Cohen et al. (1980). For related structures, see: Li et al. (2005); Tanaka & Ajiki (2005).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Intermolecular C—H···π (red dotted lines) and S···S (green dotted lines) interactions in the title compound. All H atoms except those related to intermolecular interactions have been omitted for clarity. Cg is the centroid of the C1/C2/C3/C4/C5/C6 ring. [Symmetry codes: (i) x, -1+y, z]

Bis(benzylsulfanyl)methane top

Crystal data top

C₁₅H₁₆S₂	F(000) = 552
M_r = 260.40	D_x = 1.303 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7825 reflections
a = 5.5146 (1) Å	θ = 2.7–28.4°
b = 12.2628 (3) Å	µ = 0.38 mm⁻¹
c = 20.0128 (5) Å	T = 173 K
β = 101.156 (1)°	Block, colourless
V = 1327.78 (5) Å³	0.22 × 0.15 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3335 independent reflections
Radiation source: fine-focus sealed tube	2977 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→16
T_min = 0.922, T_max = 0.946	l = −24→26
12942 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0369P)² + 0.4363P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3335 reflections	Δρ_max = 0.30 e Å⁻³
155 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (2)

Crystal data top

C₁₅H₁₆S₂	V = 1327.78 (5) Å³
M_r = 260.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.5146 (1) Å	µ = 0.38 mm⁻¹
b = 12.2628 (3) Å	T = 173 K
c = 20.0128 (5) Å	0.22 × 0.15 × 0.15 mm
β = 101.156 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3335 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2977 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.946	R_int = 0.033
12942 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.04	Δρ_max = 0.30 e Å⁻³
3335 reflections	Δρ_min = −0.29 e Å⁻³
155 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
S1	0.63212 (6)	0.46872 (3)	0.430321 (16)	0.03123 (10)
S2	0.80471 (6)	0.43167 (3)	0.294901 (16)	0.03327 (11)
C1	0.7958 (2)	0.73297 (11)	0.47700 (6)	0.0318 (3)
H1	0.6990	0.7130	0.5095	0.038*
C2	0.9857 (3)	0.80750 (11)	0.49456 (7)	0.0369 (3)
H2	1.0197	0.8377	0.5391	0.044*
C3	1.1262 (3)	0.83815 (11)	0.44745 (8)	0.0376 (3)
H3	1.2579	0.8887	0.4597	0.045*
C4	1.0740 (3)	0.79496 (11)	0.38253 (7)	0.0371 (3)
H4	1.1678	0.8170	0.3498	0.045*
C5	0.8848 (2)	0.71936 (11)	0.36495 (6)	0.0324 (3)
H5	0.8508	0.6897	0.3203	0.039*
C6	0.7447 (2)	0.68671 (10)	0.41215 (6)	0.0269 (2)
C7	0.5451 (2)	0.60237 (11)	0.39470 (7)	0.0319 (3)
H7A	0.4995	0.5959	0.3445	0.038*
H7B	0.3970	0.6276	0.4114	0.038*
C8	0.8761 (2)	0.43180 (11)	0.38662 (7)	0.0303 (3)
H8A	0.9344	0.3579	0.4019	0.036*
H8B	1.0158	0.4826	0.4014	0.036*
C9	0.5351 (2)	0.34398 (11)	0.27868 (6)	0.0320 (3)
H9A	0.3992	0.3808	0.2956	0.038*
H9B	0.4822	0.3351	0.2288	0.038*
C10	0.5717 (2)	0.23235 (10)	0.31064 (6)	0.0263 (2)
C11	0.7532 (2)	0.16136 (11)	0.29690 (6)	0.0309 (3)
H11	0.8598	0.1839	0.2675	0.037*
C12	0.7799 (2)	0.05829 (11)	0.32574 (7)	0.0327 (3)
H12	0.9041	0.0106	0.3158	0.039*
C13	0.6268 (2)	0.02439 (11)	0.36880 (7)	0.0324 (3)
H13	0.6452	−0.0463	0.3885	0.039*
C14	0.4464 (3)	0.09429 (11)	0.38292 (7)	0.0344 (3)
H14	0.3406	0.0716	0.4125	0.041*
C15	0.4196 (2)	0.19762 (11)	0.35389 (7)	0.0307 (3)
H15	0.2951	0.2451	0.3639	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.03604 (18)	0.02830 (18)	0.03133 (17)	−0.00231 (12)	0.01147 (13)	−0.00010 (12)
S2	0.04070 (19)	0.02943 (18)	0.03283 (17)	−0.00462 (13)	0.01497 (13)	0.00064 (12)
C1	0.0353 (6)	0.0333 (7)	0.0270 (6)	−0.0013 (5)	0.0064 (5)	0.0029 (5)
C2	0.0422 (7)	0.0336 (7)	0.0322 (6)	−0.0033 (6)	0.0008 (5)	0.0007 (5)
C3	0.0336 (7)	0.0275 (7)	0.0505 (8)	−0.0018 (5)	0.0048 (6)	0.0079 (6)
C4	0.0395 (7)	0.0316 (7)	0.0445 (7)	0.0056 (6)	0.0185 (6)	0.0113 (6)
C5	0.0390 (7)	0.0293 (6)	0.0299 (6)	0.0089 (5)	0.0093 (5)	0.0039 (5)
C6	0.0270 (6)	0.0240 (6)	0.0285 (5)	0.0060 (5)	0.0026 (4)	0.0028 (4)
C7	0.0269 (6)	0.0302 (6)	0.0368 (6)	0.0046 (5)	0.0018 (5)	−0.0015 (5)
C8	0.0263 (6)	0.0291 (6)	0.0349 (6)	0.0019 (5)	0.0042 (5)	0.0005 (5)
C9	0.0345 (6)	0.0295 (6)	0.0302 (6)	−0.0001 (5)	0.0019 (5)	0.0020 (5)
C10	0.0264 (5)	0.0257 (6)	0.0251 (5)	−0.0019 (5)	0.0009 (4)	−0.0029 (4)
C11	0.0309 (6)	0.0340 (7)	0.0288 (6)	−0.0006 (5)	0.0085 (5)	−0.0032 (5)
C12	0.0320 (6)	0.0297 (6)	0.0359 (6)	0.0043 (5)	0.0051 (5)	−0.0072 (5)
C13	0.0355 (6)	0.0231 (6)	0.0364 (6)	−0.0019 (5)	0.0011 (5)	−0.0015 (5)
C14	0.0347 (7)	0.0305 (7)	0.0399 (7)	−0.0041 (5)	0.0120 (5)	0.0012 (5)
C15	0.0277 (6)	0.0281 (6)	0.0374 (6)	0.0011 (5)	0.0087 (5)	−0.0027 (5)

Geometric parameters (Å, º) top

S1—C8	1.7988 (13)	C7—H7B	0.9900
S1—C7	1.8144 (14)	C8—H8A	0.9900
S2—C8	1.8013 (13)	C8—H8B	0.9900
S2—C9	1.8125 (14)	C9—C10	1.5079 (17)
C1—C2	1.3831 (19)	C9—H9A	0.9900
C1—C6	1.3942 (17)	C9—H9B	0.9900
C1—H1	0.9500	C10—C15	1.3841 (18)
C2—C3	1.383 (2)	C10—C11	1.3934 (18)
C2—H2	0.9500	C11—C12	1.3854 (19)
C3—C4	1.381 (2)	C11—H11	0.9500
C3—H3	0.9500	C12—C13	1.382 (2)
C4—C5	1.389 (2)	C12—H12	0.9500
C4—H4	0.9500	C13—C14	1.383 (2)
C5—C6	1.3898 (18)	C13—H13	0.9500
C5—H5	0.9500	C14—C15	1.3899 (19)
C6—C7	1.5016 (18)	C14—H14	0.9500
C7—H7A	0.9900	C15—H15	0.9500

C8—S1—C7	101.67 (6)	S2—C8—H8A	108.0
C8—S2—C9	101.13 (6)	S1—C8—H8B	108.0
C2—C1—C6	120.80 (12)	S2—C8—H8B	108.0
C2—C1—H1	119.6	H8A—C8—H8B	107.2
C6—C1—H1	119.6	C10—C9—S2	115.14 (9)
C1—C2—C3	120.19 (13)	C10—C9—H9A	108.5
C1—C2—H2	119.9	S2—C9—H9A	108.5
C3—C2—H2	119.9	C10—C9—H9B	108.5
C4—C3—C2	119.65 (13)	S2—C9—H9B	108.5
C4—C3—H3	120.2	H9A—C9—H9B	107.5
C2—C3—H3	120.2	C15—C10—C11	118.46 (12)
C3—C4—C5	120.26 (13)	C15—C10—C9	119.80 (11)
C3—C4—H4	119.9	C11—C10—C9	121.73 (11)
C5—C4—H4	119.9	C12—C11—C10	120.68 (12)
C4—C5—C6	120.61 (12)	C12—C11—H11	119.7
C4—C5—H5	119.7	C10—C11—H11	119.7
C6—C5—H5	119.7	C13—C12—C11	120.38 (12)
C5—C6—C1	118.46 (12)	C13—C12—H12	119.8
C5—C6—C7	121.28 (11)	C11—C12—H12	119.8
C1—C6—C7	120.25 (12)	C12—C13—C14	119.43 (12)
C6—C7—S1	113.86 (8)	C12—C13—H13	120.3
C6—C7—H7A	108.8	C14—C13—H13	120.3
S1—C7—H7A	108.8	C13—C14—C15	120.14 (13)
C6—C7—H7B	108.8	C13—C14—H14	119.9
S1—C7—H7B	108.8	C15—C14—H14	119.9
H7A—C7—H7B	107.7	C10—C15—C14	120.91 (12)
S1—C8—S2	117.33 (7)	C10—C15—H15	119.5
S1—C8—H8A	108.0	C14—C15—H15	119.5

C6—C1—C2—C3	0.7 (2)	C9—S2—C8—S1	−53.62 (9)
C1—C2—C3—C4	0.8 (2)	C8—S2—C9—C10	−55.87 (11)
C2—C3—C4—C5	−1.4 (2)	S2—C9—C10—C15	123.62 (11)
C3—C4—C5—C6	0.4 (2)	S2—C9—C10—C11	−57.57 (14)
C4—C5—C6—C1	1.09 (18)	C15—C10—C11—C12	0.22 (18)
C4—C5—C6—C7	−177.97 (12)	C9—C10—C11—C12	−178.61 (11)
C2—C1—C6—C5	−1.67 (19)	C10—C11—C12—C13	−0.15 (19)
C2—C1—C6—C7	177.40 (12)	C11—C12—C13—C14	0.00 (19)
C5—C6—C7—S1	103.14 (12)	C12—C13—C14—C15	0.1 (2)
C1—C6—C7—S1	−75.91 (14)	C11—C10—C15—C14	−0.12 (18)
C8—S1—C7—C6	−64.96 (10)	C9—C10—C15—C14	178.72 (12)
C7—S1—C8—S2	−56.40 (9)	C13—C14—C15—C10	0.0 (2)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cgⁱ	0.95	2.85	3.71	151

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆S₂
M_r	260.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	5.5146 (1), 12.2628 (3), 20.0128 (5)
β (°)	101.156 (1)
V (Å³)	1327.78 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.22 × 0.15 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.922, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	12942, 3335, 2977
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 1.04
No. of reflections	3335
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cgⁱ	0.95	2.85	3.71	151

Symmetry code: (i) x, y−1, z.

Acknowledgements

This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2010-0016386).

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cohen, T., Ruffner, R. J., Shull, D. W., Fogel, E. R. & Falck, J. R. (1980). Org. Synth. 59, 202–212. CAS Google Scholar
Li, J.-R., Bu, X.-H., Jiao, J., Du, X.-H. & Zhang, R.-H. (2005). Dalton Trans. pp. 464–474. Web of Science CSD CrossRef Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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