3,5-Dibromo-2-[2,5-dibut­oxy-4-(3,5-dibromo­thio­phen-2-yl)phen­yl]thio­phene

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

doi:10.1107/S1600536811045235

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3183

https://doi.org/10.1107/S1600536811045235

Open

access

3,5-Dibromo-2-[2,5-dibutoxy-4-(3,5-dibromothiophen-2-yl)phenyl]thiophene

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

^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, ^cDepartment of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia, and ^dFuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Selangor, Malaysia
^*Correspondence e-mail: mbkassim@ukm.my

(Received 25 October 2011; accepted 28 October 2011; online 5 November 2011)

The title molecule, C₂₂H₂₂Br₄O₂S₂, is centrosymmetric with an inversion centre located at the centre of the benzene ring. The 3,5-dibromothiophene groups are twisted relative to the benzene ring, making a dihedral angle of 41.43 (9)°.

Related literature

The title compound belongs to the family of arylthiophenes, compounds frequently used as electroluminescent oligomers to produce polymers for LED applications. For a related structure and background references, see: Promarak & Ruchirawat (2007 ); Huang et al. (2007 ). For related structures, see: Li et al. (2008 ); Kuriger et al. (2008 ); Ali et al. (2008 ).

Experimental

Crystal data

C₂₂H₂₂Br₄O₂S₂
M_r = 702.16
Monoclinic, P 2₁ /c
a = 13.0156 (3) Å
b = 7.8157 (2) Å
c = 12.2264 (2) Å
β = 101.027 (2)°
V = 1220.78 (5) Å³
Z = 2
Cu Kα radiation
μ = 9.79 mm⁻¹
T = 150 K
0.24 × 0.10 × 0.07 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ) T_min = 0.202, T_max = 0.547
12067 measured reflections
2349 independent reflections
2272 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.084
S = 1.10
2349 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction, Abingdon, England.]$ ); data reduction: CrysAlis RED; 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/S1600536811045235/gk2422sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045235/gk2422Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045235/gk2422Isup3.cml

checkCIF report

Comment top

Brominated thiophene-phenylene oligomer with enhanced solubility characteristics due to the presence of alkyloxy substituents such as in the title compound, (I) is an important intermediate to engineer soluble electroluminescent oligomers and polymers for LED applications (Huang et al., 2007).

The structure of I is centrosymmetric with an inversion centre located at the centre of the benzene ring. The mean plane of the central unit [O1/C1/C5/C6/C7/C8/C9/O1A/C1A/C5A/C6A/C7A/C8A/C9A] (A) is approximately planar with the highest deviation of ^±0.023 (2)° for atoms O1/O1A and the 3,5-dibromothiophene rings are twisted relative to the plane forming a dihedral angle of 41.43 (9)°. Half of the butyloxy groups lie above/below the mean plane A and the mean planes of [C8C9C10C11A] and [C8AC9AC10AC11A] make a dihedral angle of 59.5 (3)° with A. The torsion angle C8-C9-C10-C11 is 179.7 (3)° and this conformation does not allow for stacking interactions of the aromatic units. Thus quenching of the luminescent effect for polymer generated from this oligomer can be avoided (Fig. 2).

Related literature top

The title compound belongs to the family of arylthiophenes, compounds frequently used as electroluminescent oligomers to produce polymers for LED applications. For a related structure and background references, see: Promarak & Ruchirawat (2007); Huang et al. (2007). For related structures, see: Li et al. (2008); Kuriger et al. (2008); Ali et al. (2008).

Experimental top

The title compound was prepared according to previously published procedure (Promarak & Ruchirawat, 2007) with a slight modification. N-Bromosuccinimide (0.58 g, 3.26 mmol) was added into a solution of 1,4-bis(thiophen-2-yl)-2,5-bis(butyloxy)benzene (0.60 g, 1.55 mmol) in THF:DMF (v/v=1:1). The mixture was heated under reflux overnight and allowed to cool to ambient temperature prior to addition of water. The compound was extracted into dichloromethane, washed with water and brine solution, dried over anhydrous MgSO₄ and the solvent was removed by evaporation. Recrystallization of the product from hot dichloromethane solution afforded crystals suitable for single-crystal X-ray diffraction (yield: 63%; m.p. 417-419 K).

Structure description top

The title compound belongs to the family of arylthiophenes, compounds frequently used as electroluminescent oligomers to produce polymers for LED applications. For a related structure and background references, see: Promarak & Ruchirawat (2007); Huang et al. (2007). For related structures, see: Li et al. (2008); Kuriger et al. (2008); Ali et al. (2008).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (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 c-axis.

3,5-Dibromo-2-[2,5-dibutoxy-4-(3,5-dibromothiophen-2-yl)phenyl]thiophene top

Crystal data top

C₂₂H₂₂Br₄O₂S₂	F(000) = 684
M_r = 702.16	D_x = 1.910 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 417–419 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 13.0156 (3) Å	Cell parameters from 7985 reflections
b = 7.8157 (2) Å	θ = 3–71°
c = 12.2264 (2) Å	µ = 9.79 mm⁻¹
β = 101.027 (2)°	T = 150 K
V = 1220.78 (5) Å³	Prismatic, yellow
Z = 2	0.24 × 0.10 × 0.07 mm

Data collection top

Oxford Diffraction Gemini diffractometer	2349 independent reflections
Radiation source: fine-focus sealed tube	2272 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω/2θ scans	θ_max = 71.0°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −15→15
T_min = 0.202, T_max = 0.547	k = −9→9
12067 measured reflections	l = −14→14

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)] = 0.030	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0574P)² + 0.8587P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2349 reflections	Δρ_max = 0.98 e Å⁻³
138 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0057 (3)

Crystal data top

C₂₂H₂₂Br₄O₂S₂	V = 1220.78 (5) Å³
M_r = 702.16	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 13.0156 (3) Å	µ = 9.79 mm⁻¹
b = 7.8157 (2) Å	T = 150 K
c = 12.2264 (2) Å	0.24 × 0.10 × 0.07 mm
β = 101.027 (2)°

Data collection top

Oxford Diffraction Gemini diffractometer	2349 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	2272 reflections with I > 2σ(I)
T_min = 0.202, T_max = 0.547	R_int = 0.037
12067 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.10	Δρ_max = 0.98 e Å⁻³
2349 reflections	Δρ_min = −0.54 e Å⁻³
138 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
Br1	0.85564 (2)	0.22645 (4)	0.97981 (2)	0.02292 (14)
Br2	0.43160 (2)	0.45620 (4)	0.82956 (2)	0.01904 (14)
S1	0.74092 (5)	0.36060 (9)	0.74910 (5)	0.01532 (18)
O1	0.70059 (14)	0.6197 (2)	0.57663 (15)	0.0142 (4)
C1	0.60951 (19)	0.4183 (3)	0.7216 (2)	0.0119 (5)
C2	0.56937 (19)	0.3982 (3)	0.8164 (2)	0.0122 (5)
C3	0.6403 (2)	0.3333 (3)	0.9103 (2)	0.0143 (5)
H3	0.6239	0.3128	0.9799	0.017*
C4	0.7353 (2)	0.3055 (3)	0.8837 (2)	0.0143 (5)
C5	0.5550 (2)	0.4615 (3)	0.6079 (2)	0.0115 (5)
C6	0.6011 (2)	0.5643 (3)	0.5364 (2)	0.0113 (5)
C7	0.4545 (2)	0.3963 (3)	0.5690 (2)	0.0125 (5)
H7	0.4243	0.3250	0.6150	0.015*
C8	0.7491 (2)	0.7284 (3)	0.5067 (2)	0.0158 (5)
H8A	0.7077	0.8311	0.4876	0.019*
H8B	0.7549	0.6692	0.4384	0.019*
C9	0.8561 (2)	0.7736 (4)	0.5713 (3)	0.0193 (6)
H9A	0.8917	0.8437	0.5247	0.023*
H9B	0.8963	0.6692	0.5884	0.023*
C10	0.8543 (2)	0.8692 (4)	0.6796 (3)	0.0278 (7)
H10A	0.8147	0.9742	0.6627	0.033*
H10B	0.8186	0.7995	0.7264	0.033*
C11	0.9630 (3)	0.9124 (5)	0.7433 (4)	0.0411 (9)
H11A	1.0016	0.8086	0.7632	0.062*
H11B	0.9574	0.9744	0.8097	0.062*
H11C	0.9987	0.9813	0.6974	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0157 (2)	0.0312 (2)	0.0196 (2)	0.00459 (11)	−0.00230 (13)	0.00655 (11)
Br2	0.01321 (19)	0.0258 (2)	0.0200 (2)	0.00462 (10)	0.00798 (13)	0.00194 (10)
S1	0.0078 (3)	0.0252 (4)	0.0130 (3)	0.0008 (2)	0.0021 (2)	0.0026 (2)
O1	0.0071 (8)	0.0178 (9)	0.0168 (9)	−0.0044 (7)	−0.0001 (7)	0.0041 (7)
C1	0.0075 (11)	0.0121 (11)	0.0160 (13)	−0.0016 (9)	0.0024 (10)	0.0002 (10)
C2	0.0096 (12)	0.0118 (11)	0.0157 (12)	−0.0010 (9)	0.0037 (9)	−0.0015 (10)
C3	0.0155 (13)	0.0152 (13)	0.0130 (12)	0.0008 (10)	0.0045 (10)	0.0012 (10)
C4	0.0131 (13)	0.0151 (12)	0.0133 (12)	0.0009 (10)	−0.0010 (10)	0.0026 (10)
C5	0.0097 (12)	0.0128 (12)	0.0124 (12)	0.0005 (9)	0.0034 (10)	0.0003 (9)
C6	0.0078 (12)	0.0104 (12)	0.0160 (12)	−0.0019 (9)	0.0032 (10)	−0.0024 (9)
C7	0.0099 (12)	0.0130 (12)	0.0157 (12)	−0.0018 (10)	0.0048 (9)	0.0023 (9)
C8	0.0102 (13)	0.0181 (13)	0.0193 (13)	−0.0037 (10)	0.0036 (11)	0.0050 (10)
C9	0.0080 (13)	0.0205 (14)	0.0289 (15)	−0.0028 (10)	0.0025 (11)	0.0040 (11)
C10	0.0136 (15)	0.0281 (16)	0.0406 (19)	−0.0038 (11)	0.0021 (13)	−0.0073 (13)
C11	0.0219 (17)	0.039 (2)	0.057 (2)	−0.0070 (15)	−0.0077 (16)	−0.0178 (18)

Geometric parameters (Å, º) top

Br1—C4	1.874 (3)	C7—C6ⁱ	1.387 (4)
Br2—C2	1.886 (3)	C7—H7	0.9300
S1—C4	1.716 (3)	C8—C9	1.506 (4)
S1—C1	1.738 (3)	C8—H8A	0.9700
O1—C6	1.365 (3)	C8—H8B	0.9700
O1—C8	1.434 (3)	C9—C10	1.524 (4)
C1—C2	1.368 (4)	C9—H9A	0.9700
C1—C5	1.474 (4)	C9—H9B	0.9700
C2—C3	1.422 (4)	C10—C11	1.517 (4)
C3—C4	1.355 (4)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C5—C7	1.400 (4)	C11—H11A	0.9600
C5—C6	1.404 (4)	C11—H11B	0.9600
C6—C7ⁱ	1.387 (4)	C11—H11C	0.9600

C4—S1—C1	91.70 (13)	O1—C8—H8A	110.3
C6—O1—C8	117.94 (19)	C9—C8—H8A	110.3
C2—C1—C5	129.2 (2)	O1—C8—H8B	110.3
C2—C1—S1	109.12 (19)	C9—C8—H8B	110.3
C5—C1—S1	121.31 (19)	H8A—C8—H8B	108.5
C1—C2—C3	115.5 (2)	C8—C9—C10	113.8 (2)
C1—C2—Br2	124.6 (2)	C8—C9—H9A	108.8
C3—C2—Br2	119.89 (19)	C10—C9—H9A	108.8
C4—C3—C2	110.2 (2)	C8—C9—H9B	108.8
C4—C3—H3	124.9	C10—C9—H9B	108.8
C2—C3—H3	124.9	H9A—C9—H9B	107.7
C3—C4—S1	113.4 (2)	C11—C10—C9	112.8 (3)
C3—C4—Br1	126.5 (2)	C11—C10—H10A	109.0
S1—C4—Br1	120.03 (15)	C9—C10—H10A	109.0
C7—C5—C6	118.7 (2)	C11—C10—H10B	109.0
C7—C5—C1	119.1 (2)	C9—C10—H10B	109.0
C6—C5—C1	122.2 (2)	H10A—C10—H10B	107.8
O1—C6—C7ⁱ	123.7 (2)	C10—C11—H11A	109.5
O1—C6—C5	116.5 (2)	C10—C11—H11B	109.5
C7ⁱ—C6—C5	119.8 (2)	H11A—C11—H11B	109.5
C6ⁱ—C7—C5	121.5 (2)	C10—C11—H11C	109.5
C6ⁱ—C7—H7	119.2	H11A—C11—H11C	109.5
C5—C7—H7	119.2	H11B—C11—H11C	109.5
O1—C8—C9	107.2 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Br2	0.93	2.80	3.289 (2)	114

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂Br₄O₂S₂
M_r	702.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	13.0156 (3), 7.8157 (2), 12.2264 (2)
β (°)	101.027 (2)
V (Å³)	1220.78 (5)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	9.79
Crystal size (mm)	0.24 × 0.10 × 0.07

Data collection
Diffractometer	Oxford Diffraction Gemini
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.202, 0.547
No. of measured, independent and observed [I > 2σ(I)] reflections	12067, 2349, 2272
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.613

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.10
No. of reflections	2349
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.54

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).

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) for TCH.

References

Ali, B. F., Al-Far, R. H. & Haddad, S. F. (2008). Acta Cryst. E64, m751–m752. Web of Science CSD CrossRef IUCr Journals Google Scholar
Huang, S.-P., Huang, G.-S. & Chen, S.-A. (2007). Synth. Met. 157, 863–871. Web of Science CrossRef CAS Google Scholar
Kuriger, T. M., Moratti, S. C. & Simpson, J. (2008). Acta Cryst. E64, o709. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, Y.-F., Xu, C., Cen, F.-F., Wang, Z.-Q. & Zhang, Y.-Q. (2008). Acta Cryst. E64, o1930. Web of Science CrossRef IUCr Journals Google Scholar
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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.