2,2′-[2,5-Bis(hex­yloxy)-1,4-phenyl­ene]dithio­phene

Teh, C.H.; Mat Salleh, M.; Mohamed Tahir, M.I.; Daik, R.; Kassim, M.B.

doi:10.1107/S160053681202404X

organic compounds

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Volume 68| Part 7| July 2012| Page o1976

https://doi.org/10.1107/S160053681202404X

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2,2′-[2,5-Bis(hexyloxy)-1,4-phenylene]dithiophene

Chin Hoong Teh,^a Muhammad Mat Salleh,^b Mohamed Ibrahim Mohamed Tahir,^c Rusli Daik ^a and Mohammad B. Kassim ^a ^*

^aSchool of Chemical Sciences & Food Technology, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia, ^bInstitut of Microengineering and Nanoelectronics (IMEN), Universiti Kebangsaan Malaysia, UKM 43600 Bangi, Selangor, Malaysia, and ^cDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 25 May 2012; accepted 26 May 2012; online 2 June 2012)

The asymmetric unit of the title compound, C₂₆H₃₄O₂S₂, comprises one half-molecule located on an inversion centre. The thiophene groups are twisted relative to the benzene ring, making a dihedral angle of 5.30 (7)°, and the n-hexyl groups are in a fully extended conformation. In the crystal, there are short C—H⋯π contacts involving the thiophene groups.

Related literature

For the synthesis and general background references, see: Carle et al. (2010 ); Promarak & Ruchirawat (2007 ); Bouachrine et al. (2002 ).

Experimental

Crystal data

C₂₆H₃₄O₂S₂
M_r = 442.65
Monoclinic, P 2₁ /c
a = 12.2996 (3) Å
b = 5.4298 (1) Å
c = 17.6872 (4) Å
β = 103.982 (2)°
V = 1146.23 (4) Å³
Z = 2
Cu Kα radiation
μ = 2.25 mm⁻¹
T = 150 K
0.26 × 0.11 × 0.03 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ) T_min = 0.592, T_max = 0.935
8010 measured reflections
2216 independent reflections
2018 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.113
S = 1.04
2216 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the S1, C4–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Cg1ⁱ	0.93	2.85	3.5809 (16)	137
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); 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, PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681202404X/gk2496sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202404X/gk2496Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681202404X/gk2496Isup3.cml

checkCIF report

Comment top

Thiophene-phenylene-thiophene unit, as in the title compound, is an interesting material to produce soluble electroluminescent materials for LED applications (Bouachrine et al., 2002) and making photovoltaic devices (Carle et al., 2010). The solubility characteristic for the title compound in organic solvents was enhanced by the presence of dialkyloxy groups on the phenylene fragment.

The molecule of the title compound is shown in Fig. 1 and crystal packing projection along the b axis is shown in Fig. 2.

Related literature top

For the synthesis and general background references, see: Carle et al. (2010); Promarak & Ruchirawat (2007); Bouachrine et al. (2002).

Experimental top

The preparation of title compound was adapted from previously published procedure with a slight modification (Promarak & Ruchirawat, 2007). Aqueous sodium carbonate solution (2M, 10.5 ml) was added into a solution of 2,5-dibromo-1,4-bis(hexyloxy)benzene (1.50 g, 3.44 mmol) in dry THF prior to addition of Pd(PPh₃)₄ (0.21 g) catalyst. This was followed by the addition of 2-thiophene boronic acid (1.32 g, 10.32 mmol) and the mixture was heated under reflux overnight in dry N₂ atmosphere and allowed to cool to ambient temperature prior to addition of water. The product was extracted into CH₂Cl₂ and the organic phase was combined, washed with water and brine solution, followed by drying over anhydrous MgSO₄. The solvent was evaporated using rotary evaporator and the product was further recrystallized from ethanol/ethyl acetate to afford crystals suitable for single-crystal X-ray diffraction (yield: 80%).

Structure description top

The molecule of the title compound is shown in Fig. 1 and crystal packing projection along the b axis is shown in Fig. 2.

For the synthesis and general background references, see: Carle et al. (2010); Promarak & Ruchirawat (2007); Bouachrine et al. (2002).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Symmetry code for atoms with the A label: -x, 1 - y, 1 - z.
	Fig. 2. Crystal packing of the title compound viewed down the b-axis.

2,2'-[2,5-Bis(hexyloxy)-1,4-phenylene]dithiophene top

Crystal data top

C₂₆H₃₄O₂S₂	F(000) = 476
M_r = 442.65	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 369–367 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 12.2996 (3) Å	Cell parameters from 3985 reflections
b = 5.4298 (1) Å	θ = 4–71°
c = 17.6872 (4) Å	µ = 2.25 mm⁻¹
β = 103.982 (2)°	T = 150 K
V = 1146.23 (4) Å³	Thin plate, colourless
Z = 2	0.26 × 0.11 × 0.03 mm

Data collection top

Oxford Diffraction Gemini diffractometer	2216 independent reflections
Radiation source: fine-focus sealed tube	2018 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 71.3°, θ_min = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	h = −15→14
T_min = 0.592, T_max = 0.935	k = −6→6
8010 measured reflections	l = −21→15

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0739P)² + 0.5049P] where P = (F_o² + 2F_c²)/3
2216 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₆H₃₄O₂S₂	V = 1146.23 (4) Å³
M_r = 442.65	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 12.2996 (3) Å	µ = 2.25 mm⁻¹
b = 5.4298 (1) Å	T = 150 K
c = 17.6872 (4) Å	0.26 × 0.11 × 0.03 mm
β = 103.982 (2)°

Data collection top

Oxford Diffraction Gemini diffractometer	2216 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	2018 reflections with I > 2σ(I)
T_min = 0.592, T_max = 0.935	R_int = 0.028
8010 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.04	Δρ_max = 0.40 e Å⁻³
2216 reflections	Δρ_min = −0.22 e Å⁻³
137 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer 1986) with a nominal stability of 0.1 K.

Cosier, J. & Glazer, A.M., (1986)., J. Appl. Cryst. 105 107.

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	0.29977 (3)	0.23308 (7)	0.14406 (2)	0.02015 (17)
O1	0.33781 (9)	0.3460 (2)	0.00566 (6)	0.0185 (3)
C1	0.41842 (12)	0.1767 (3)	0.00089 (8)	0.0151 (3)
C2	0.44944 (12)	0.0140 (3)	0.06456 (8)	0.0146 (3)
C3	0.46770 (12)	0.1612 (3)	−0.06175 (8)	0.0153 (3)
H3	0.4451	0.2703	−0.1031	0.018*
C4	0.39762 (12)	0.0159 (3)	0.13132 (8)	0.0144 (3)
C5	0.41723 (12)	−0.1539 (3)	0.19221 (8)	0.0163 (3)
H5	0.4667	−0.2856	0.1962	0.020*
C6	0.35315 (13)	−0.1034 (3)	0.24751 (9)	0.0190 (3)
H6	0.3560	−0.1990	0.2916	0.023*
C7	0.28728 (13)	0.0999 (3)	0.22898 (9)	0.0205 (3)
H7	0.2408	0.1595	0.2592	0.025*
C8	0.30066 (12)	0.5135 (3)	−0.05794 (8)	0.0161 (3)
H8A	0.2722	0.4229	−0.1059	0.019*
H8B	0.3624	0.6160	−0.0643	0.019*
C9	0.20894 (12)	0.6715 (3)	−0.03966 (8)	0.0162 (3)
H9A	0.2394	0.7674	0.0069	0.019*
H9B	0.1504	0.5663	−0.0294	0.019*
C10	0.15873 (13)	0.8453 (3)	−0.10717 (9)	0.0173 (3)
H10A	0.2181	0.9460	−0.1184	0.021*
H10B	0.1269	0.7482	−0.1532	0.021*
C11	0.06820 (13)	1.0129 (3)	−0.09008 (9)	0.0180 (3)
H11A	0.1007	1.1141	−0.0451	0.022*
H11B	0.0102	0.9122	−0.0770	0.022*
C12	0.01499 (13)	1.1804 (3)	−0.15839 (9)	0.0206 (3)
H12A	0.0732	1.2796	−0.1718	0.025*
H12B	−0.0182	1.0791	−0.2032	0.025*
C13	−0.07480 (13)	1.3507 (3)	−0.14123 (10)	0.0237 (4)
H13A	−0.1337	1.2538	−0.1291	0.036*
H13B	−0.1050	1.4511	−0.1861	0.036*
H13C	−0.0422	1.4544	−0.0977	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0231 (3)	0.0238 (3)	0.0156 (2)	0.00695 (14)	0.00873 (17)	0.00228 (13)
O1	0.0210 (6)	0.0222 (6)	0.0139 (5)	0.0084 (4)	0.0074 (4)	0.0046 (4)
C1	0.0131 (7)	0.0172 (7)	0.0143 (7)	0.0013 (6)	0.0021 (5)	−0.0007 (6)
C2	0.0135 (7)	0.0185 (7)	0.0117 (7)	−0.0007 (6)	0.0028 (5)	−0.0012 (5)
C3	0.0166 (7)	0.0174 (7)	0.0115 (7)	0.0015 (6)	0.0022 (5)	0.0024 (5)
C4	0.0126 (7)	0.0175 (7)	0.0124 (7)	0.0002 (5)	0.0016 (5)	−0.0023 (5)
C5	0.0158 (7)	0.0220 (8)	0.0119 (7)	−0.0011 (6)	0.0049 (6)	−0.0027 (6)
C6	0.0197 (7)	0.0247 (8)	0.0128 (7)	−0.0018 (6)	0.0042 (6)	0.0007 (6)
C7	0.0211 (8)	0.0286 (8)	0.0138 (7)	0.0016 (6)	0.0079 (6)	−0.0008 (6)
C8	0.0175 (7)	0.0189 (7)	0.0116 (7)	0.0033 (6)	0.0030 (5)	0.0018 (5)
C9	0.0165 (7)	0.0184 (7)	0.0139 (7)	0.0018 (6)	0.0040 (6)	−0.0001 (6)
C10	0.0184 (7)	0.0188 (7)	0.0146 (7)	0.0028 (6)	0.0039 (6)	0.0008 (6)
C11	0.0188 (7)	0.0181 (7)	0.0170 (7)	0.0019 (6)	0.0041 (6)	−0.0003 (6)
C12	0.0193 (8)	0.0235 (8)	0.0193 (8)	0.0048 (6)	0.0054 (6)	0.0026 (6)
C13	0.0207 (8)	0.0236 (8)	0.0257 (8)	0.0060 (6)	0.0037 (6)	0.0011 (7)

Geometric parameters (Å, º) top

S1—C7	1.7071 (15)	C8—H8A	0.9700
S1—C4	1.7380 (15)	C8—H8B	0.9700
O1—C1	1.3697 (18)	C9—C10	1.530 (2)
O1—C8	1.4326 (17)	C9—H9A	0.9700
C1—C3	1.388 (2)	C9—H9B	0.9700
C1—C2	1.409 (2)	C10—C11	1.524 (2)
C2—C3ⁱ	1.404 (2)	C10—H10A	0.9700
C2—C4	1.471 (2)	C10—H10B	0.9700
C3—C2ⁱ	1.404 (2)	C11—C12	1.527 (2)
C3—H3	0.9300	C11—H11A	0.9700
C4—C5	1.394 (2)	C11—H11B	0.9700
C5—C6	1.423 (2)	C12—C13	1.526 (2)
C5—H5	0.9300	C12—H12A	0.9700
C6—C7	1.362 (2)	C12—H12B	0.9700
C6—H6	0.9300	C13—H13A	0.9600
C7—H7	0.9300	C13—H13B	0.9600
C8—C9	1.513 (2)	C13—H13C	0.9600

C7—S1—C4	92.24 (7)	C8—C9—H9A	109.4
C1—O1—C8	118.42 (11)	C10—C9—H9A	109.4
O1—C1—C3	123.50 (14)	C8—C9—H9B	109.4
O1—C1—C2	115.58 (13)	C10—C9—H9B	109.4
C3—C1—C2	120.92 (14)	H9A—C9—H9B	108.0
C3ⁱ—C2—C1	117.07 (13)	C11—C10—C9	112.96 (12)
C3ⁱ—C2—C4	119.49 (13)	C11—C10—H10A	109.0
C1—C2—C4	123.42 (13)	C9—C10—H10A	109.0
C1—C3—C2ⁱ	122.00 (14)	C11—C10—H10B	109.0
C1—C3—H3	119.0	C9—C10—H10B	109.0
C2ⁱ—C3—H3	119.0	H10A—C10—H10B	107.8
C5—C4—C2	126.00 (13)	C10—C11—C12	113.12 (13)
C5—C4—S1	110.17 (11)	C10—C11—H11A	109.0
C2—C4—S1	123.82 (11)	C12—C11—H11A	109.0
C4—C5—C6	112.47 (14)	C10—C11—H11B	109.0
C4—C5—H5	123.8	C12—C11—H11B	109.0
C6—C5—H5	123.8	H11A—C11—H11B	107.8
C7—C6—C5	112.76 (14)	C13—C12—C11	113.32 (13)
C7—C6—H6	123.6	C13—C12—H12A	108.9
C5—C6—H6	123.6	C11—C12—H12A	108.9
C6—C7—S1	112.35 (12)	C13—C12—H12B	108.9
C6—C7—H7	123.8	C11—C12—H12B	108.9
S1—C7—H7	123.8	H12A—C12—H12B	107.7
O1—C8—C9	107.75 (11)	C12—C13—H13A	109.5
O1—C8—H8A	110.2	C12—C13—H13B	109.5
C9—C8—H8A	110.2	H13A—C13—H13B	109.5
O1—C8—H8B	110.2	C12—C13—H13C	109.5
C9—C8—H8B	110.2	H13A—C13—H13C	109.5
H8A—C8—H8B	108.5	H13B—C13—H13C	109.5
C8—C9—C10	111.36 (12)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S1, C4–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cg1ⁱⁱ	0.93	2.85	3.5809 (16)	137

Symmetry code: (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₆H₃₄O₂S₂
M_r	442.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	12.2996 (3), 5.4298 (1), 17.6872 (4)
β (°)	103.982 (2)
V (Å³)	1146.23 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.25
Crystal size (mm)	0.26 × 0.11 × 0.03

Data collection
Diffractometer	Oxford Diffraction Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)
T_min, T_max	0.592, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	8010, 2216, 2018
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.113, 1.04
No. of reflections	2216
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.22

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S1, C4–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Cg1ⁱ	0.93	2.85	3.5809 (16)	137

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia for research grants UKM-GUP-BTT-07–26–178 and UKM-FST-06-FRGS0095–2010. This work was also supported by a National Science Fellowship (NSF) to TCH.

References

Bouachrine, M., Lere-Porte, J.-P., Moreau, J. J. E., Spirau, F. S., da Silva, R. A., Lmimouni, K., Ouchani, L. & Dufour, C. (2002). Synth. Met. 126, 241–244. Web of Science CrossRef CAS Google Scholar
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Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England. Google Scholar
Promarak, V. & Ruchirawat, S. (2007). Tetrahedron, 63, 1602–1609. Web of Science CrossRef CAS Google Scholar
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Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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