1,2-Bis(4-ethynylphen­yl)disulfane

Xiao, Q.; Liu, R.; Li, Y.-H.; Chen, H.-B.; Zhu, H.-J.

doi:10.1107/S1600536810004721

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o606

doi:10.1107/S1600536810004721

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1,2-Bis(4-ethynylphenyl)disulfane

Qi Xiao,^a Rui Liu,^a Yu-Hao Li,^a Hong-Bin Chen ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhjnjut@hotmail.com

(Received 24 January 2010; accepted 6 February 2010; online 13 February 2010)

In the title compound, C₁₆H₁₀S₂, the S atoms are almost coplanar with the benzene rings to which they are bonded [deviations of 0.092 (1) and 0.022 (1) Å from their respective ring planes]. The benzene rings enclose a dihedral angle of 79.17 (3)°. An intramolecular C—H⋯S hydrogen bond results in the formation of a five-membered ring. In the crystal structure, molecules are stacked parallel to the a axis direction. π–π interactions between benzene rings are present, with a face-to-face stacking distance of 3.622 (10) Å.

Related literature

For bond-length data, see: Allen et al. (1987 ). For the synthetic procedure, see Yonezawa et al. (2008 ).

Experimental

Crystal data

C₁₆H₁₀S₂
M_r = 266.36
Triclinic, $[P \overline 1]$
a = 5.981 (1) Å
b = 8.881 (2) Å
c = 13.269 (3) Å
α = 94.92 (3)°
β = 99.29 (3)°
γ = 104.45 (3)°
V = 667.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 293 K
0.40 × 0.40 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.864, T_max = 0.896
2887 measured reflections
2620 independent reflections
1969 reflections with I > 2σ(I)
R_int = 0.033
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.194
S = 1.01
2620 reflections
169 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 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
C13—H13A⋯S1	0.93	2.71	3.216 (5)	115

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ); 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.

Supporting information

Crystal structure: contains datablocks I, XQ. DOI: 10.1107/S1600536810004721/im2180sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004721/im2180Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is a kind of aromatic acetylide organic intermediate which can be used for many fields such as molecular electronic materials, organometallic chemistry etc. (Yonezawa et al., 2008). We herein report its crystal structure.

In the molecule of (I), (Fig.1), the bond lengths and angles are within normal ranges (Allen et al., 1987). S atoms are situated in the same plane as the benzene rings they are bonded to. Rings A (C3—C8) and B (C11—C16) are, of course, planar and they enclose a dihedral angle of 79.17 (3) °. An intramolecular C—H···S hydrogen bond (Table 1) results in the formation of a five-membered ring C (S1/S2/C14/C13/H13A). The distance between atoms S2 and H5A is 2.91 Å, which is significantly longer than the hydrogen bond between atoms S1 and H13A.

As can be seen from the packing diagram, (Fig. 2), the molecules are stacked along the a axis. There are also the π-π interactions of benzene rings with a face-to-face stacking distance of 3.622 Å.

Related literature top

For bond-length data, see: Allen et al. (1987). For the synthetic procedure, see Yonezawa et al. (2008).

Experimental top

The title compound, (I) was prepared by a literature method (Yonezawa et al., 2008). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.5 g) in hexane (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo,1995); 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

	Fig. 1. Molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I). Hydrogen bonds are shown as dashed lines.

1,2-bis(4-ethynylphenyl)disulfane top

Crystal data top

C₁₆H₁₀S₂	Z = 2
M_r = 266.36	F(000) = 276
Triclinic, P1	D_x = 1.325 Mg m⁻³
Hall symbol: -P 1	Melting point: 391 K
a = 5.981 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.881 (2) Å	Cell parameters from 25 reflections
c = 13.269 (3) Å	θ = 10–13°
α = 94.92 (3)°	µ = 0.38 mm⁻¹
β = 99.29 (3)°	T = 293 K
γ = 104.45 (3)°	Block, colourless
V = 667.7 (2) Å³	0.40 × 0.40 × 0.30 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1969 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 26.0°, θ_min = 1.6°
ω/2θ scans	h = −7→7
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
T_min = 0.864, T_max = 0.896	l = 0→16
2887 measured reflections	3 standard reflections every 200 reflections
2620 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.060P)² + 2.P] where P = (F_o² + 2F_c²)/3
2620 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.50 e Å⁻³
2 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₆H₁₀S₂	γ = 104.45 (3)°
M_r = 266.36	V = 667.7 (2) Å³
Triclinic, P1	Z = 2
a = 5.981 (1) Å	Mo Kα radiation
b = 8.881 (2) Å	µ = 0.38 mm⁻¹
c = 13.269 (3) Å	T = 293 K
α = 94.92 (3)°	0.40 × 0.40 × 0.30 mm
β = 99.29 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1969 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.033
T_min = 0.864, T_max = 0.896	3 standard reflections every 200 reflections
2887 measured reflections	intensity decay: none
2620 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	2 restraints
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.50 e Å⁻³
2620 reflections	Δρ_min = −0.40 e Å⁻³
169 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	0.0903 (2)	0.50232 (15)	0.20304 (9)	0.0594 (4)
C1	0.8307 (10)	0.2056 (7)	0.5708 (4)	0.0674 (13)
S2	−0.1535 (2)	0.31363 (17)	0.11850 (10)	0.0619 (4)
C2	0.7075 (8)	0.2523 (6)	0.5110 (4)	0.0561 (11)
C3	0.5594 (8)	0.3096 (5)	0.4359 (3)	0.0479 (10)
C4	0.3177 (9)	0.2406 (6)	0.4127 (4)	0.0606 (12)
H4A	0.2522	0.1573	0.4461	0.073*
C5	0.1745 (8)	0.2953 (6)	0.3402 (4)	0.0571 (11)
H5A	0.0137	0.2475	0.3242	0.069*
C6	0.2705 (8)	0.4209 (5)	0.2916 (3)	0.0476 (10)
C7	0.5073 (8)	0.4891 (6)	0.3143 (4)	0.0575 (11)
H7A	0.5722	0.5718	0.2803	0.069*
C8	0.6516 (8)	0.4362 (6)	0.3876 (4)	0.0578 (11)
H8A	0.8116	0.4863	0.4042	0.069*
C9	0.3291 (10)	0.0564 (7)	−0.3034 (4)	0.0686 (14)
C10	0.2502 (8)	0.0917 (6)	−0.2347 (4)	0.0561 (11)
C11	0.1571 (8)	0.1440 (5)	−0.1475 (3)	0.0503 (10)
C12	0.2959 (8)	0.2639 (5)	−0.0736 (3)	0.0522 (10)
H12A	0.4508	0.3089	−0.0791	0.063*
C13	0.2091 (8)	0.3179 (6)	0.0079 (4)	0.0567 (11)
H13A	0.3057	0.3986	0.0570	0.068*
C14	−0.0207 (8)	0.2532 (5)	0.0175 (3)	0.0490 (10)
C15	−0.1597 (8)	0.1311 (5)	−0.0558 (4)	0.0542 (11)
H15A	−0.3133	0.0845	−0.0493	0.065*
C16	−0.0744 (8)	0.0782 (6)	−0.1376 (3)	0.0542 (11)
H16A	−0.1714	−0.0022	−0.1869	0.065*
H9	0.385 (8)	0.019 (5)	−0.362 (2)	0.065*
H1	0.947 (6)	0.176 (6)	0.617 (3)	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0706 (8)	0.0593 (7)	0.0513 (7)	0.0280 (6)	0.0044 (5)	0.0062 (5)
C1	0.069 (3)	0.071 (3)	0.062 (3)	0.021 (3)	0.006 (3)	0.012 (3)
S2	0.0527 (7)	0.0807 (9)	0.0534 (7)	0.0229 (6)	0.0062 (5)	0.0069 (6)
C2	0.055 (3)	0.060 (3)	0.049 (3)	0.014 (2)	0.004 (2)	0.002 (2)
C3	0.051 (2)	0.055 (2)	0.042 (2)	0.023 (2)	0.0102 (18)	0.0059 (18)
C4	0.059 (3)	0.064 (3)	0.060 (3)	0.017 (2)	0.010 (2)	0.018 (2)
C5	0.044 (2)	0.062 (3)	0.059 (3)	0.011 (2)	0.001 (2)	0.006 (2)
C6	0.050 (2)	0.045 (2)	0.046 (2)	0.0144 (18)	0.0069 (18)	0.0012 (18)
C7	0.059 (3)	0.058 (3)	0.057 (3)	0.013 (2)	0.013 (2)	0.017 (2)
C8	0.047 (2)	0.063 (3)	0.057 (3)	0.006 (2)	0.004 (2)	0.010 (2)
C9	0.072 (3)	0.070 (3)	0.068 (3)	0.024 (3)	0.021 (3)	0.005 (3)
C10	0.059 (3)	0.056 (3)	0.053 (3)	0.017 (2)	0.004 (2)	0.009 (2)
C11	0.053 (3)	0.053 (2)	0.049 (2)	0.021 (2)	0.0062 (19)	0.0157 (19)
C12	0.046 (2)	0.058 (3)	0.050 (2)	0.014 (2)	0.0022 (19)	0.007 (2)
C13	0.043 (2)	0.067 (3)	0.053 (3)	0.010 (2)	−0.0027 (19)	0.005 (2)
C14	0.057 (3)	0.054 (2)	0.040 (2)	0.023 (2)	0.0075 (18)	0.0115 (18)
C15	0.040 (2)	0.060 (3)	0.057 (3)	0.010 (2)	−0.0013 (19)	0.010 (2)
C16	0.052 (3)	0.058 (3)	0.048 (2)	0.016 (2)	−0.0040 (19)	0.001 (2)

Geometric parameters (Å, º) top

S1—C6	1.786 (4)	C8—H8A	0.9300
S1—S2	2.030 (2)	C9—C10	1.147 (7)
C1—C2	1.169 (7)	C9—H9	0.959 (10)
C1—H1	0.956 (10)	C10—C11	1.452 (7)
S2—C14	1.774 (4)	C11—C12	1.379 (6)
C2—C3	1.436 (6)	C11—C16	1.394 (6)
C3—C8	1.382 (6)	C12—C13	1.374 (6)
C3—C4	1.393 (6)	C12—H12A	0.9300
C4—C5	1.384 (6)	C13—C14	1.382 (6)
C4—H4A	0.9300	C13—H13A	0.9300
C5—C6	1.383 (6)	C14—C15	1.386 (6)
C5—H5A	0.9300	C15—C16	1.368 (7)
C6—C7	1.366 (6)	C15—H15A	0.9300
C7—C8	1.386 (6)	C16—H16A	0.9300
C7—H7A	0.9300

C6—S1—S2	104.69 (15)	C7—C8—H8A	119.8
C2—C1—H1	173 (3)	C10—C9—H9	175 (3)
C14—S2—S1	105.55 (17)	C9—C10—C11	177.3 (6)
C1—C2—C3	178.8 (5)	C12—C11—C16	118.5 (4)
C8—C3—C4	118.7 (4)	C12—C11—C10	120.2 (4)
C8—C3—C2	121.0 (4)	C16—C11—C10	121.4 (4)
C4—C3—C2	120.3 (4)	C13—C12—C11	121.0 (4)
C5—C4—C3	120.4 (4)	C13—C12—H12A	119.5
C5—C4—H4A	119.8	C11—C12—H12A	119.5
C3—C4—H4A	119.8	C12—C13—C14	120.6 (4)
C6—C5—C4	120.0 (4)	C12—C13—H13A	119.7
C6—C5—H5A	120.0	C14—C13—H13A	119.7
C4—C5—H5A	120.0	C13—C14—C15	118.5 (4)
C7—C6—C5	119.7 (4)	C13—C14—S2	124.8 (4)
C7—C6—S1	118.7 (3)	C15—C14—S2	116.7 (4)
C5—C6—S1	121.5 (3)	C16—C15—C14	121.0 (4)
C6—C7—C8	120.6 (4)	C16—C15—H15A	119.5
C6—C7—H7A	119.7	C14—C15—H15A	119.5
C8—C7—H7A	119.7	C15—C16—C11	120.4 (4)
C3—C8—C7	120.5 (4)	C15—C16—H16A	119.8
C3—C8—H8A	119.8	C11—C16—H16A	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···S1	0.93	2.71	3.216 (5)	115

Experimental details

Crystal data
Chemical formula	C₁₆H₁₀S₂
M_r	266.36
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.981 (1), 8.881 (2), 13.269 (3)
α, β, γ (°)	94.92 (3), 99.29 (3), 104.45 (3)
V (Å³)	667.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.864, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	2887, 2620, 1969
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.194, 1.01
No. of reflections	2620
No. of parameters	169
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.40

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···S1	0.9300	2.7100	3.216 (5)	115.00

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yonezawa, T., Uchida, K., Yamanoi, Y., Horinouchi, S., Terasaki, N. & Nishihara, H. (2008). Phys. Chem. Chem. Phys. 10, 6925–6927. Web of Science CrossRef PubMed CAS Google Scholar