[(Dibenzo[b,d]thio­phen-4-yl)tellan­yl]methane­thiol

Liang, Z.-Q.; Tao, X.-T.

doi:10.1107/S160053681100273X

organic compounds

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Volume 67| Part 2| February 2011| Page o519

doi:10.1107/S160053681100273X

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[(Dibenzo[b,d]thiophen-4-yl)tellanyl]methanethiol

Zuo-Qin Liang ^a and Xu-Tang Tao ^a ^*

^aState Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: lam051227@mail.sdu.edu.cn

(Received 15 January 2011; accepted 20 January 2011; online 29 January 2011)

In the title compound, C₁₃H₁₀S₂Te, the dibenzothiophene moiety is almost planar, the maximum atomic deviation being 0.055 (5) Å. The two Te—C bonds are nearly perpendicular to each other with a C—Te—C bond angle of 93.0 (2)°. An intermolecular C—H⋯π interaction is present between the methylene group and thiophene ring.

Related literature

For general background to the field-effect transistors of organotellurium derivatives, see: Inokuchi et al. (1987 ). For related structures, see: Kobayashi et al. (2005 ).

Experimental

Crystal data

C₁₃H₁₀S₂Te
M_r = 357.93
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.49518 (12) Å
b = 12.1422 (3) Å
c = 19.0529 (5) Å
V = 1271.27 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.64 mm⁻¹
T = 293 K
0.58 × 0.45 × 0.31 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.310, T_max = 0.495
5117 measured reflections
2509 independent reflections
2248 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.083
S = 0.98
2509 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.55 e Å⁻³
Absolute structure: Flack (1983 ), 975 Friedel pairs
Flack parameter: 0.01 (3)

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the thiophene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯Cgⁱ	0.97	2.90	3.846 (6)	166
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100273X/xu5144sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100273X/xu5144Isup2.hkl

checkCIF report

Comment top

The design and synthesis of high-performance organic semiconductor materials have been an active topic in the area of field-effect transistors. Recently, organotellurium compounds have received significant attention due to the high charge carrier mobility (Inokuchi et al., 1987). In this paper, we report the synthesis and the crystal structure of the title compound (I).

The asymmetric unit of the title compound is shown in Fig. 1. The dibenzothiophene group possesses perfect planarity: the dihedral angle between the two phenyls is 4.11°. The two Te—C bonds are nearly perpendicular to each other with a C—Te—C bond angle of 93.0 (2)°. In the packing structure (Fig. 2), the molecules are packed into molecular columns along the a axis through intermolecular Te···π interactions between the tellurium atom and the phenyl ring (C7—C12). The contact distance of Te···C9 is 3.68 (5) Å, that of Te···C10 is 3.47 (5) Å, and that of Te···C11 is 3.73 (7) Å. These contact distances are significantly shorter than the sum of the van der Waals radii of tellurium and aromatic carbon atoms (Kobayashi et al., 2005). The molecular columns are connected together by intermolecular C···S and S···S interactions. The contact distances of C13···S1 and S1···S2 are 3.43 (5) Å and 3.51 (2) Å, respectively, which are obviously shorter than the sum of the corresponding van der Waals radii. There are no classic hydrogen bonds in the crystal structure.

Related literature top

For general background to the field-effect transistors of organotellurium derivatives, see: Inokuchi et al. (1987). For related structures, see: Kobayashi et al. (2005).

Experimental top

Addition of a 1.6 M solution of n-BuLi in hexane (8.50 ml, 13.6 mmol) to the THF solution of dibenzothiophene (2.50 g, 13.6 mmol) at room temperature under an Ar atmosphere. The reaction mixture was stirred for 2 h, and then tellurium powder (1.70 g, 13.3 mmol) was added. After 3 h, the reaction mixture was poured into a beaker containing 200 ml cold distilled water and oxidized by passing oxygen at a moderate rate for 1 h. The organic solvent was evaporated, and the suspension was extracted with dichloromethane. The organic extracts were washed by brine, and dried by anhydrous CaCl₂. After the solvent was removed, the crude product was chromatographed on silica gel using petroleum as eluent to give the title compound (0.27 g, yield 5.56%). Single crystals suitable for X-ray diffraction were obtained by very slow evaporation of a chloroform/ethanol solution.

Computing details top

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO CCD (Oxford Diffraction, 2009); data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Stacking diagram of (I), viewed down the a axis, showing intermolecular Te···π, C···S and S···S interactions (dashed lines). The hydrogen atoms have been omitted for clarity.

{8-thiatricyclo[7.4.0.0^2,7]trideca-1(9),2(7),3,5,10,12-hexaen-6- yltellanyl}methanethiol top

Crystal data top

C₁₃H₁₀S₂Te	D_x = 1.870 Mg m⁻³
M_r = 357.93	Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3403 reflections
a = 5.49518 (12) Å	θ = 3.5–28.8°
b = 12.1422 (3) Å	µ = 2.64 mm⁻¹
c = 19.0529 (5) Å	T = 293 K
V = 1271.27 (6) Å³	Block, colorless
Z = 4	0.58 × 0.45 × 0.31 mm
F(000) = 688

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2509 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2248 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 16.0355 pixels mm^-1	θ_max = 26.4°, θ_min = 3.5°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	k = −15→7
T_min = 0.310, T_max = 0.495	l = −21→24
5117 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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0502P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
2509 reflections	Δρ_max = 0.81 e Å⁻³
146 parameters	Δρ_min = −0.55 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 975 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (3)

Crystal data top

C₁₃H₁₀S₂Te	V = 1271.27 (6) Å³
M_r = 357.93	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.49518 (12) Å	µ = 2.64 mm⁻¹
b = 12.1422 (3) Å	T = 293 K
c = 19.0529 (5) Å	0.58 × 0.45 × 0.31 mm

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	2509 independent reflections
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	2248 reflections with I > 2σ(I)
T_min = 0.310, T_max = 0.495	R_int = 0.054
5117 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.81 e Å⁻³
S = 0.98	Δρ_min = −0.55 e Å⁻³
2509 reflections	Absolute structure: Flack (1983), 975 Friedel pairs
146 parameters	Absolute structure parameter: 0.01 (3)
0 restraints

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

	x	y	z	U_iso*/U_eq
Te1	0.65007 (6)	0.83287 (3)	0.120133 (19)	0.05366 (13)
S1	0.8260 (2)	0.97156 (10)	−0.03248 (6)	0.0466 (3)
S2	1.0630 (4)	0.65872 (16)	0.17855 (9)	0.0778 (5)
H2	0.9995	0.5698	0.1991	0.093*
C12	0.9348 (8)	0.9486 (4)	0.1106 (2)	0.0401 (10)
C8	1.1849 (8)	1.0679 (3)	0.0346 (2)	0.0373 (9)
C4	1.3695 (10)	1.1778 (4)	−0.0677 (3)	0.0486 (11)
H4	1.4968	1.2065	−0.0412	0.058*
C9	1.3274 (10)	1.0953 (4)	0.0922 (3)	0.0466 (11)
H9	1.4611	1.1415	0.0868	0.056*
C2	1.1594 (11)	1.1620 (5)	−0.1780 (3)	0.0551 (12)
H2A	1.1483	1.1809	−0.2252	0.066*
C13	0.8876 (11)	0.6962 (4)	0.1038 (3)	0.0570 (15)
H13A	0.7910	0.6332	0.0895	0.068*
H13B	0.9975	0.7137	0.0656	0.068*
C3	1.3448 (11)	1.2056 (4)	−0.1376 (3)	0.0545 (12)
H3	1.4548	1.2543	−0.1579	0.065*
C6	1.0149 (8)	1.0623 (4)	−0.0788 (2)	0.0394 (10)
C7	0.9883 (8)	0.9950 (4)	0.0445 (2)	0.0381 (10)
C11	1.0743 (9)	0.9798 (4)	0.1662 (3)	0.0471 (12)
H11	1.0404	0.9519	0.2105	0.057*
C1	0.9912 (9)	1.0912 (4)	−0.1496 (3)	0.0486 (12)
H1	0.8648	1.0631	−0.1767	0.058*
C10	1.2698 (10)	1.0539 (5)	0.1574 (3)	0.0534 (13)
H10	1.3611	1.0750	0.1962	0.064*
C5	1.2002 (7)	1.1060 (4)	−0.0370 (2)	0.0380 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Te1	0.04305 (17)	0.05162 (19)	0.0663 (2)	0.00382 (16)	0.01498 (15)	0.01196 (17)
S1	0.0380 (5)	0.0542 (7)	0.0475 (6)	−0.0110 (6)	−0.0028 (5)	0.0017 (5)
S2	0.1032 (13)	0.0683 (10)	0.0621 (9)	0.0296 (10)	−0.0107 (8)	0.0080 (8)
C12	0.041 (2)	0.036 (2)	0.042 (3)	0.0116 (18)	0.006 (2)	0.004 (2)
C8	0.035 (2)	0.030 (2)	0.048 (2)	0.0031 (18)	0.001 (2)	−0.0034 (18)
C4	0.047 (3)	0.041 (2)	0.058 (3)	−0.010 (3)	0.003 (2)	−0.003 (2)
C9	0.044 (2)	0.042 (2)	0.054 (3)	−0.003 (2)	−0.008 (2)	−0.004 (2)
C2	0.066 (3)	0.055 (3)	0.045 (2)	0.011 (4)	0.010 (3)	0.006 (2)
C13	0.067 (4)	0.043 (3)	0.061 (3)	0.009 (2)	−0.006 (3)	−0.005 (2)
C3	0.058 (3)	0.045 (3)	0.060 (3)	−0.006 (3)	0.013 (3)	0.010 (2)
C6	0.036 (2)	0.036 (2)	0.046 (3)	0.0048 (19)	0.008 (2)	−0.007 (2)
C7	0.034 (2)	0.029 (2)	0.052 (3)	0.0093 (17)	0.001 (2)	−0.001 (2)
C11	0.060 (3)	0.040 (3)	0.041 (2)	0.018 (2)	0.000 (2)	0.004 (2)
C1	0.049 (3)	0.047 (3)	0.050 (3)	−0.004 (2)	−0.003 (2)	−0.001 (2)
C10	0.057 (3)	0.052 (3)	0.051 (3)	0.004 (3)	−0.015 (2)	−0.010 (2)
C5	0.036 (2)	0.033 (2)	0.045 (2)	0.0048 (17)	0.0011 (19)	−0.0028 (19)

Geometric parameters (Å, º) top

Te1—C12	2.111 (5)	C9—H9	0.9300
Te1—C13	2.134 (5)	C9—C10	1.376 (8)
S1—C6	1.753 (5)	C2—H2A	0.9300
S1—C7	1.739 (5)	C2—C3	1.382 (8)
S2—H2	1.2000	C2—C1	1.374 (8)
S2—C13	1.778 (6)	C13—H13A	0.9700
C12—C7	1.412 (7)	C13—H13B	0.9700
C12—C11	1.360 (7)	C3—H3	0.9300
C8—C9	1.389 (6)	C6—C1	1.399 (7)
C8—C7	1.409 (6)	C6—C5	1.397 (6)
C8—C5	1.443 (6)	C11—H11	0.9300
C4—H4	0.9300	C11—C10	1.411 (8)
C4—C3	1.381 (8)	C1—H1	0.9300
C4—C5	1.403 (7)	C10—H10	0.9300

Te1—C13—H13A	108.6	H13A—C13—H13B	107.6
Te1—C13—H13B	108.6	C3—C4—H4	120.4
S2—C13—Te1	114.5 (3)	C3—C4—C5	119.3 (5)
S2—C13—H13A	108.6	C3—C2—H2A	119.4
S2—C13—H13B	108.6	C6—C1—H1	120.9
C12—Te1—C13	93.0 (2)	C6—C5—C8	112.0 (4)
C12—C7—S1	125.5 (3)	C6—C5—C4	118.8 (4)
C12—C11—H11	119.5	C7—S1—C6	91.0 (2)
C12—C11—C10	121.0 (5)	C7—C12—Te1	119.8 (3)
C8—C9—H9	120.1	C7—C8—C5	111.9 (4)
C8—C7—S1	112.5 (3)	C11—C12—Te1	122.4 (4)
C8—C7—C12	122.0 (4)	C11—C12—C7	117.8 (4)
C4—C3—C2	121.0 (5)	C11—C10—H10	119.5
C4—C3—H3	119.5	C1—C2—H2A	119.4
C4—C5—C8	129.2 (4)	C1—C2—C3	121.1 (5)
C9—C8—C7	118.5 (4)	C1—C6—S1	126.0 (4)
C9—C8—C5	129.6 (4)	C10—C9—C8	119.7 (5)
C9—C10—C11	121.0 (5)	C10—C9—H9	120.1
C9—C10—H10	119.5	C10—C11—H11	119.5
C2—C3—H3	119.5	C5—C4—H4	120.4
C2—C1—C6	118.3 (5)	C5—C6—S1	112.5 (4)
C2—C1—H1	120.9	C5—C6—C1	121.5 (5)
C13—S2—H2	109.5

Te1—C12—C7—S1	4.0 (5)	C6—S1—C7—C12	178.1 (4)
Te1—C12—C7—C8	−176.4 (3)	C6—S1—C7—C8	−1.5 (3)
Te1—C12—C11—C10	177.3 (4)	C7—S1—C6—C1	−177.9 (4)
S1—C6—C1—C2	−178.6 (4)	C7—S1—C6—C5	1.9 (3)
S1—C6—C5—C8	−1.9 (5)	C7—C12—C11—C10	−1.6 (7)
S1—C6—C5—C4	178.4 (4)	C7—C8—C9—C10	−1.9 (7)
C12—Te1—C13—S2	78.3 (3)	C7—C8—C5—C4	−179.5 (5)
C12—C11—C10—C9	−1.0 (8)	C7—C8—C5—C6	0.7 (5)
C8—C9—C10—C11	2.9 (8)	C11—C12—C7—S1	−177.0 (3)
C9—C8—C7—S1	178.9 (3)	C11—C12—C7—C8	2.5 (6)
C9—C8—C7—C12	−0.7 (6)	C1—C2—C3—C4	1.1 (8)
C9—C8—C5—C4	2.6 (8)	C1—C6—C5—C8	178.0 (4)
C9—C8—C5—C6	−177.2 (4)	C1—C6—C5—C4	−1.8 (7)
C13—Te1—C12—C7	91.8 (4)	C5—C8—C9—C10	175.8 (5)
C13—Te1—C12—C11	−87.1 (4)	C5—C8—C7—S1	0.7 (5)
C3—C4—C5—C8	−178.2 (5)	C5—C8—C7—C12	−178.9 (4)
C3—C4—C5—C6	1.6 (7)	C5—C4—C3—C2	−1.3 (8)
C3—C2—C1—C6	−1.2 (8)	C5—C6—C1—C2	1.6 (7)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Cgⁱ	0.97	2.90	3.846 (6)	166

Symmetry code: (i) x−1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀S₂Te
M_r	357.93
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.49518 (12), 12.1422 (3), 19.0529 (5)
V (Å³)	1271.27 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.64
Crystal size (mm)	0.58 × 0.45 × 0.31

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)
T_min, T_max	0.310, 0.495
No. of measured, independent and observed [I > 2σ(I)] reflections	5117, 2509, 2248
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.083, 0.98
No. of reflections	2509
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.55
Absolute structure	Flack (1983), 975 Friedel pairs
Absolute structure parameter	0.01 (3)

Computer programs: CrysAlis PRO CCD (Oxford Diffraction, 2009), CrysAlis PRO RED (Oxford Diffraction, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the thiophene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Cgⁱ	0.97	2.90	3.846 (6)	166

Symmetry code: (i) x−1/2, −y+3/2, −z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant Nos. 50721002 and 50802054).

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Inokuchi, H., Imaeda, K., Enoki, T., Mori, T., Maruyama, Y., Saito, G., Okada, N., Yamochi, H., Seki, K., Higuchi, Y. & Yasuoka, N. (1987). Nature (London), 329, 39–40. CSD CrossRef CAS Web of Science Google Scholar
Kobayashi, K., Masu, H., Shuto, A. & Yamaguchi, K. (2005). Chem. Mater. 17, 6666–6673. Web of Science CSD CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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