1,4-Bis(4-bromo­but­oxy)benzene

Maragatham, G.; Selvarani, S.; Rajakumar, P.; Lakshmi, S.

doi:10.1107/S2414314617010045

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 7| July 2017| x171004

https://doi.org/10.1107/S2414314617010045

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1,4-Bis(4-bromobutoxy)benzene

Gunasekaran Maragatham,^a Sivasamy Selvarani,^b Perumal Rajakumar ^b and Srinivasakannan Lakshmi ^a ^*

^aDepartment of Physics, S.D.N.B. Vaishnav College for Women, Chromepet, Chennai 600 044, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: lakssdnbvc@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 19 June 2017; accepted 6 July 2017; online 18 July 2017)

The complete molecule of the title compound, C₁₄H₂₀Br₂O₂, is generated by crystallographic inversion symmetry and the 4-bromobutoxy side chain adopts an extended conformation. In the crystal, weak C—H⋯π interactions are observed, which help to consolidate a herringbone packing motif.

Keywords: crystal structure; bromobutoxy; C—H⋯ π interactions.

CCDC reference: 1560690

Structure description

Compounds with alkyloxy substituents act as intermediates to engineer soluble electroluminescent oligomers and polymers for LED applications (Huang et al., 2007 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound.

The asymmetric unit, contains one-half of the molecule, while the other half is generated through crystallographic inversion symmetry [symmetry code: (i) −x, 1 − y, −z] (Fig. 1). The bromoalkoxyl tail is roughly co-planar with the attached benzene ring with a C6—C5—O1—C4 torsion angle of −2.2 (3)°. The bromoalkoxyl tail adopts an extended conformation as shown by the C5—O1—C4—C3, O1—C4—C3—C2, C4—C3—C2—C1 and C3—C2—C1—Br1 torsion angles of −179.55 (19), −176.29 (18), 177.5 (2) and 179.19 (17)°, respectively. The packing of the molecules features weak C—H⋯π interactions (Table 1), which lead to a herringbone arrangement when viewed along [100] (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯Cg1ⁱ	0.97	2.84	3.664 (3)	144
Symmetry code: (i) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level [symmetry code: (a) −x, 1 − y, −z].

Figure 2
The packing of the molecules viewed along the a-axis direction.

Synthesis and crystallization

A mixture of (1.0 equiv.) of resorcinol and potassium carbonate (2.0 equiv.) in acetone (50 ml) was stirred for 15 minutes at 60° C. 1,4-Dibromobutane (2.1 equiv.) was added to the reaction mixture and stirred at 60° C for 7 h. After completion of the reaction, the solvent was removed under reduced pressure and the residue was extracted with CHCl₃ (3 × 100 ml), washed with water (2 × 100 ml), brine (150 ml) and dried over anhydrous Na₂SO₄, filtered and concentrated in vacuo. The residue obtained was purified by column chromatography using CHCl₃:hexane (1:9) as eluent to afford the title compound as a white solid, which was recrystallized from methanol solution to yield colourless blocks.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₂₀Br₂O₂
M_r	380.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	9.0845 (10), 5.3436 (5), 15.3509 (15)
β (°)	95.567 (4)
V (Å³)	741.68 (13)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.46
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.525, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	7040, 1310, 1126
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.052, 1.06
No. of reflections	1310
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.33
Computer programs: APEX2 and SAINT (Bruker, 2004), SIR92 (Altomare et al., 1993 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Bruno et al., 2002 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1560690

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010045/hb4156sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010045/hb4156Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617010045/hb4156Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2010).

1,4-Bis(4-bromobutoxy)benzene top

Crystal data top

C₁₄H₂₀Br₂O₂	F(000) = 380
M_r = 380.12	D_x = 1.702 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0845 (10) Å	Cell parameters from 3047 reflections
b = 5.3436 (5) Å	θ = 2.7–24.9°
c = 15.3509 (15) Å	µ = 5.46 mm⁻¹
β = 95.567 (4)°	T = 296 K
V = 741.68 (13) Å³	Block, colourless
Z = 2	0.35 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1310 independent reflections
Radiation source: fine-focus sealed tube	1126 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and φ scan	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.525, T_max = 0.745	k = −6→6
7040 measured reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.0214P)² + 0.4039P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1310 reflections	Δρ_max = 0.32 e Å⁻³
82 parameters	Δρ_min = −0.33 e Å⁻³

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. H atoms were included in the refinement at calculated positions (C—H = 0.93–0.98 Å), with U_iso(H) = 1.2Ueq(C) using a riding-model approximation.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.0397 (3)	1.4815 (5)	−0.34901 (18)	0.0487 (7)
H1A	−0.1220	1.5707	−0.3277	0.058*
H1B	−0.0796	1.3642	−0.3934	0.058*
C2	0.0404 (3)	1.3397 (4)	−0.27508 (15)	0.0354 (6)
H2A	0.0812	1.4561	−0.2306	0.043*
H2B	0.1216	1.2472	−0.2962	0.043*
C3	−0.0642 (3)	1.1585 (4)	−0.23511 (15)	0.0343 (6)
H3A	−0.1431	1.2523	−0.2119	0.041*
H3B	−0.1085	1.0478	−0.2804	0.041*
C4	0.0151 (3)	1.0047 (4)	−0.16294 (15)	0.0323 (5)
H4A	0.0974	0.9162	−0.1845	0.039*
H4B	0.0532	1.1121	−0.1150	0.039*
C5	−0.0386 (3)	0.6709 (4)	−0.06653 (14)	0.0288 (5)
C6	0.1050 (3)	0.6624 (4)	−0.02794 (15)	0.0305 (5)
H6	0.1759	0.7708	−0.0464	0.037*
C7	0.1431 (3)	0.4919 (4)	0.03832 (14)	0.0307 (5)
H7	0.2399	0.4864	0.0642	0.037*
O1	−0.08882 (18)	0.8306 (3)	−0.13368 (11)	0.0376 (4)
Br1	0.08821 (3)	1.72008 (5)	−0.40166 (2)	0.04831 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0408 (17)	0.0559 (16)	0.0491 (16)	−0.0108 (13)	0.0028 (13)	0.0206 (13)
C2	0.0386 (15)	0.0339 (12)	0.0338 (13)	−0.0018 (11)	0.0035 (11)	0.0026 (10)
C3	0.0347 (15)	0.0358 (13)	0.0324 (13)	−0.0015 (11)	0.0027 (11)	0.0056 (10)
C4	0.0335 (14)	0.0322 (12)	0.0314 (12)	−0.0024 (10)	0.0038 (11)	0.0037 (10)
C5	0.0323 (13)	0.0283 (11)	0.0256 (12)	0.0017 (10)	0.0021 (10)	0.0006 (9)
C6	0.0274 (13)	0.0322 (12)	0.0321 (12)	−0.0037 (10)	0.0035 (10)	0.0028 (10)
C7	0.0248 (13)	0.0353 (12)	0.0313 (12)	−0.0012 (10)	−0.0001 (10)	0.0015 (10)
O1	0.0323 (10)	0.0402 (9)	0.0390 (9)	−0.0043 (8)	−0.0022 (8)	0.0147 (8)
Br1	0.0566 (2)	0.04394 (17)	0.04603 (18)	−0.00749 (13)	0.01338 (13)	0.01054 (12)

Geometric parameters (Å, º) top

C1—C2	1.494 (3)	C4—O1	1.428 (3)
C1—Br1	1.952 (2)	C4—H4A	0.9700
C1—H1A	0.9700	C4—H4B	0.9700
C1—H1B	0.9700	C5—C6	1.381 (3)
C2—C3	1.526 (3)	C5—O1	1.381 (3)
C2—H2A	0.9700	C5—C7ⁱ	1.387 (3)
C2—H2B	0.9700	C6—C7	1.384 (3)
C3—C4	1.506 (3)	C6—H6	0.9300
C3—H3A	0.9700	C7—C5ⁱ	1.387 (3)
C3—H3B	0.9700	C7—H7	0.9300

C2—C1—Br1	112.34 (19)	H3A—C3—H3B	107.9
C2—C1—H1A	109.1	O1—C4—C3	107.66 (19)
Br1—C1—H1A	109.1	O1—C4—H4A	110.2
C2—C1—H1B	109.1	C3—C4—H4A	110.2
Br1—C1—H1B	109.1	O1—C4—H4B	110.2
H1A—C1—H1B	107.9	C3—C4—H4B	110.2
C1—C2—C3	110.6 (2)	H4A—C4—H4B	108.5
C1—C2—H2A	109.5	C6—C5—O1	124.8 (2)
C3—C2—H2A	109.5	C6—C5—C7ⁱ	119.5 (2)
C1—C2—H2B	109.5	O1—C5—C7ⁱ	115.7 (2)
C3—C2—H2B	109.5	C5—C6—C7	119.7 (2)
H2A—C2—H2B	108.1	C5—C6—H6	120.2
C4—C3—C2	111.7 (2)	C7—C6—H6	120.2
C4—C3—H3A	109.3	C6—C7—C5ⁱ	120.8 (2)
C2—C3—H3A	109.3	C6—C7—H7	119.6
C4—C3—H3B	109.3	C5ⁱ—C7—H7	119.6
C2—C3—H3B	109.3	C5—O1—C4	117.18 (18)

Br1—C1—C2—C3	179.19 (17)	C5—C6—C7—C5ⁱ	0.0 (4)
C1—C2—C3—C4	177.5 (2)	C6—C5—O1—C4	−2.2 (3)
C2—C3—C4—O1	−176.29 (18)	C7ⁱ—C5—O1—C4	178.59 (18)
O1—C5—C6—C7	−179.2 (2)	C3—C4—O1—C5	−179.55 (19)
C7ⁱ—C5—C6—C7	0.0 (4)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···Cg1ⁱⁱ	0.97	2.84	3.664 (3)	144

Symmetry code: (ii) x−1/2, −y−1/2, z−3/2.

Acknowledgements

The authors thank the single-crystal XRD facility, SAIF IIT Madras, Chennai, for the data collection.

References

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