1,4-Bis[4-(tert-butyl­sulfan­yl)phen­yl]buta-1,3-diyne

Seidel, N.; Förster, S.; Seichter, W.; Weber, E.

doi:10.1107/S1600536812017710

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1543

doi:10.1107/S1600536812017710

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1,4-Bis[4-(tert-butylsulfanyl)phenyl]buta-1,3-diyne

Nadine Seidel,^a Sebastian Förster,^a Wilhelm Seichter ^a and Edwin Weber ^a ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany
^*Correspondence e-mail: edwin.weber@chemie.tu-freiberg.de

(Received 2 April 2012; accepted 20 April 2012; online 28 April 2012)

The asymmetric unit of the title compound, C₂₄H₂₆S₂, consits of one half-molecule, which is located on a center of inversion. The two benzene rings are exactly coplanar while the tert-butyl group is oriented nearly perpendicular to the ring plane [C—S—C—C = −81.14 (11)°].

Related literature

For background to this work, see: Pearson & Tour (1997 ); Kergueris et al. (1999 ). For related structures, see: Kergueris et al. (1999); Mayor et al. (2003 ). For the synthetic procedure, see: van Dijk et al. (2006 ). For the unsubstituted 1,4-diphenylbuta-1,3-diyne, see: Hori et al. (1987 ).

Experimental

Crystal data

C₂₄H₂₆S₂
M_r = 378.57
Monoclinic, P 2₁ /n
a = 13.6286 (5) Å
b = 6.4269 (2) Å
c = 14.1290 (5) Å
β = 116.937 (2)°
V = 1103.29 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 153 K
0.53 × 0.20 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.881, T_max = 0.989
11825 measured reflections
3028 independent reflections
2450 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.091
S = 1.04
3028 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017710/nc2274sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017710/nc2274Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017710/nc2274Isup3.cml

checkCIF report

Comment top

Rod-type oligo(phenyleneethynylene)s are important representatives of conjugated molecular wires (Pearson et al., 1997). Molecular rods consisting protected terminal thiol anchor groups have been embedded as passive elements in Molecular Break-Junctions (Kergueris et al., 1999). As a part of our ongoing project on the synthesis of corresponding structures, the title compound was obtained as a by-product and was identified by single-crystal X-ray diffraction. It crystallizes with one half of the molecule in the unit cell, i.e. the molecule adopts inversion symmetry. The molecule features an almost planar geometry except for the tert-butyl groups which are slightly twisted out of the plane (C(7)—S(1)—C(1)—C(2) 81.15 (14) °, C(1)—S(1)—C(7)—C(10) -67.57 (12) °). Compared with the unsubstituted 1,4-diphenylbuta-1,3-diyne (Hori et al., 1987), the position of atoms shows marginal differences. Bond distances of the ring are in the range 1.38–1.40 Å, the shortest being C(5)—C(6)=1.383 (19) Å. The angles in the ring are between 119.01 (12) and 120.47 (13) °. The C—S distance is in good agreement with the literature data [S(1)—C(1) 1.7747 (14) Å, S(1)—C(7) 1.8514 (17) Å] (Mayor et al., 2003).

Related literature top

For background to this work, see: Pearson & Tour (1997); Kergueris et al. (1999). For related structures, see: Kergueris et al. (1999); Mayor et al. (2003). For the synthetic procedure, see: van Dijk et al. (2006). For the unsubstituted 1,4-diphenylbuta-1,3-diyne, see: Hori et al. (1987).

Experimental top

The title compound has been obtained as a by-product during attempted Sonogashira cross coupling reaction of tert-butyl-(4-ethynylphenyl)sulfane with 2,6-dibromoanthra-9,10-quinone in diisopropylamine. For the synthetic procedure, see: van Dijk et al., (2006). The plate shaped crystals are colourless and stable in the air.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of the title compound with labelling showing 50% probability displacement ellipsoids for the non-H atoms. Symmetry code: i = -x+2, -y, -z+2.

1,4-Bis[4-(tert-butylsulfanyl)phenyl]buta-1,3-diyne top

Crystal data top

C₂₄H₂₆S₂	F(000) = 404
M_r = 378.57	D_x = 1.140 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.6286 (5) Å	Cell parameters from 4805 reflections
b = 6.4269 (2) Å	θ = 2.8–30.5°
c = 14.1290 (5) Å	µ = 0.25 mm⁻¹
β = 116.937 (2)°	T = 153 K
V = 1103.29 (7) Å³	Plate, colourless
Z = 2	0.53 × 0.20 × 0.05 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3028 independent reflections
Radiation source: fine-focus sealed tube	2450 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
phi and ω scans	θ_max = 29.4°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −17→18
T_min = 0.881, T_max = 0.989	k = −8→8
11825 measured reflections	l = −19→17

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0415P)² + 0.3498P] where P = (F_o² + 2F_c²)/3
3028 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₄H₂₆S₂	V = 1103.29 (7) Å³
M_r = 378.57	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.6286 (5) Å	µ = 0.25 mm⁻¹
b = 6.4269 (2) Å	T = 153 K
c = 14.1290 (5) Å	0.53 × 0.20 × 0.05 mm
β = 116.937 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3028 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2450 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.989	R_int = 0.025
11825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.04	Δρ_max = 0.35 e Å⁻³
3028 reflections	Δρ_min = −0.20 e Å⁻³
121 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

	x	y	z	U_iso*/U_eq
S1	0.93054 (2)	0.80456 (5)	0.55276 (2)	0.02231 (10)
C1	0.93335 (10)	0.62309 (18)	0.64857 (9)	0.0206 (2)
C2	0.90994 (11)	0.68270 (19)	0.73135 (10)	0.0250 (3)
H2	0.8874	0.8214	0.7343	0.030*
C3	0.91924 (11)	0.5417 (2)	0.80912 (10)	0.0261 (3)
H3	0.9019	0.5832	0.8643	0.031*
C4	0.95429 (10)	0.33764 (19)	0.80637 (10)	0.0234 (3)
C5	0.97762 (11)	0.2782 (2)	0.72369 (10)	0.0257 (3)
H5	1.0013	0.1402	0.7212	0.031*
C6	0.96658 (11)	0.41878 (19)	0.64538 (10)	0.0247 (3)
H6	0.9817	0.3760	0.5890	0.030*
C7	0.78266 (11)	0.8255 (2)	0.45814 (11)	0.0308 (3)
C8	0.73566 (15)	0.6125 (3)	0.41517 (14)	0.0523 (5)
H8A	0.7786	0.5482	0.3831	0.078*
H8B	0.6589	0.6271	0.3614	0.078*
H8C	0.7391	0.5247	0.4733	0.078*
C9	0.78203 (13)	0.9643 (3)	0.37009 (13)	0.0467 (4)
H9A	0.7060	0.9860	0.3159	0.070*
H9B	0.8241	0.8972	0.3378	0.070*
H9C	0.8155	1.0989	0.4001	0.070*
C10	0.72009 (13)	0.9298 (3)	0.51159 (14)	0.0480 (4)
H10A	0.7237	0.8416	0.5697	0.072*
H10B	0.6430	0.9492	0.4595	0.072*
H10C	0.7534	1.0653	0.5399	0.072*
C11	0.97122 (11)	0.1931 (2)	0.88969 (10)	0.0259 (3)
C12	0.98954 (11)	0.0698 (2)	0.95990 (10)	0.0265 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02344 (15)	0.02417 (15)	0.02180 (16)	0.00002 (11)	0.01242 (12)	0.00352 (11)
C1	0.0213 (5)	0.0224 (5)	0.0181 (6)	−0.0005 (4)	0.0090 (5)	0.0011 (4)
C2	0.0327 (7)	0.0210 (6)	0.0255 (6)	0.0017 (5)	0.0169 (5)	0.0000 (5)
C3	0.0347 (7)	0.0264 (6)	0.0222 (6)	0.0008 (5)	0.0173 (5)	−0.0011 (5)
C4	0.0267 (6)	0.0230 (6)	0.0205 (6)	−0.0010 (5)	0.0107 (5)	0.0013 (4)
C5	0.0330 (7)	0.0218 (6)	0.0237 (6)	0.0030 (5)	0.0141 (5)	−0.0002 (5)
C6	0.0307 (6)	0.0257 (6)	0.0212 (6)	0.0022 (5)	0.0148 (5)	−0.0005 (5)
C7	0.0244 (6)	0.0385 (7)	0.0259 (7)	0.0009 (5)	0.0083 (5)	0.0080 (6)
C8	0.0453 (9)	0.0535 (10)	0.0391 (9)	−0.0178 (8)	0.0026 (8)	−0.0021 (8)
C9	0.0375 (8)	0.0616 (11)	0.0362 (8)	0.0078 (7)	0.0125 (7)	0.0244 (8)
C10	0.0305 (8)	0.0661 (11)	0.0508 (10)	0.0153 (8)	0.0215 (7)	0.0150 (9)
C11	0.0321 (6)	0.0246 (6)	0.0235 (6)	0.0000 (5)	0.0147 (5)	−0.0011 (5)
C12	0.0340 (7)	0.0246 (6)	0.0246 (6)	0.0015 (5)	0.0167 (6)	−0.0007 (5)

Geometric parameters (Å, º) top

S1—C1	1.7740 (12)	C7—C9	1.528 (2)
S1—C7	1.8509 (13)	C7—C10	1.526 (2)
C1—C2	1.3980 (17)	C8—H8A	0.9800
C1—C6	1.3964 (17)	C8—H8B	0.9800
C2—C3	1.3852 (17)	C8—H8C	0.9800
C2—H2	0.9500	C9—H9A	0.9800
C3—C4	1.4022 (17)	C9—H9B	0.9800
C3—H3	0.9500	C9—H9C	0.9800
C4—C5	1.3957 (17)	C10—H10A	0.9800
C4—C11	1.4339 (17)	C10—H10B	0.9800
C5—C6	1.3828 (17)	C10—H10C	0.9800
C5—H5	0.9500	C11—C12	1.2042 (18)
C6—H6	0.9500	C12—C12ⁱ	1.370 (3)
C7—C8	1.517 (2)

C1—S1—C7	103.83 (6)	C9—C7—S1	103.49 (10)
C2—C1—C6	119.01 (11)	C10—C7—S1	110.13 (10)
C2—C1—S1	121.60 (9)	C7—C8—H8A	109.5
C6—C1—S1	119.27 (9)	C7—C8—H8B	109.5
C3—C2—C1	120.72 (11)	H8A—C8—H8B	109.5
C3—C2—H2	119.6	C7—C8—H8C	109.5
C1—C2—H2	119.6	H8A—C8—H8C	109.5
C2—C3—C4	119.99 (12)	H8B—C8—H8C	109.5
C2—C3—H3	120.0	C7—C9—H9A	109.5
C4—C3—H3	120.0	C7—C9—H9B	109.5
C5—C4—C3	119.25 (11)	H9A—C9—H9B	109.5
C5—C4—C11	119.79 (11)	C7—C9—H9C	109.5
C3—C4—C11	120.89 (11)	H9A—C9—H9C	109.5
C6—C5—C4	120.49 (11)	H9B—C9—H9C	109.5
C6—C5—H5	119.8	C7—C10—H10A	109.5
C4—C5—H5	119.8	C7—C10—H10B	109.5
C5—C6—C1	120.52 (11)	H10A—C10—H10B	109.5
C5—C6—H6	119.7	C7—C10—H10C	109.5
C1—C6—H6	119.7	H10A—C10—H10C	109.5
C8—C7—C9	110.82 (14)	H10B—C10—H10C	109.5
C8—C7—C10	111.40 (14)	C12—C11—C4	177.35 (14)
C9—C7—C10	110.38 (13)	C11—C12—C12ⁱ	179.74 (18)
C8—C7—S1	110.35 (11)

C7—S1—C1—C2	−81.14 (11)	C11—C4—C5—C6	−177.00 (12)
C7—S1—C1—C6	103.04 (11)	C4—C5—C6—C1	0.9 (2)
C6—C1—C2—C3	−0.12 (19)	C2—C1—C6—C5	−0.87 (19)
S1—C1—C2—C3	−175.95 (10)	S1—C1—C6—C5	175.06 (10)
C1—C2—C3—C4	1.1 (2)	C1—S1—C7—C8	−55.80 (12)
C2—C3—C4—C5	−1.11 (19)	C1—S1—C7—C9	−174.41 (11)
C2—C3—C4—C11	175.99 (12)	C1—S1—C7—C10	67.60 (12)
C3—C4—C5—C6	0.13 (19)

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₄H₂₆S₂
M_r	378.57
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	153
a, b, c (Å)	13.6286 (5), 6.4269 (2), 14.1290 (5)
β (°)	116.937 (2)
V (Å³)	1103.29 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.53 × 0.20 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.881, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	11825, 3028, 2450
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.04
No. of reflections	3028
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.20

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was performed within the Cluster of Excellence "Structure Design of Novel High-Performance Materials via Atomic Design and Defect Engineering (ADDE)" that is financially supported by the European Union (European Regional Development Fund) and by the Ministry of Science and Art of Saxony (SMWK).

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