1,3-Bis(4-bromo­but­oxy)benzene

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

doi:10.1107/S2414314617012081

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 9| September 2017| x171208

https://doi.org/10.1107/S2414314617012081

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1,3-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 H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 18 July 2017; accepted 22 August 2017; online 8 September 2017)

The whole molecule of the title compound, C₁₄H₂₀Br₂O₂, is generated by twofold rotational symmetry, with the twofold axis bisecting the benzene ring. The packing of the molecules features C—H⋯π interactions, which link the molecules to form chains along [100].

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

CCDC reference: 1570193

Structure description

Alkoxy-substituted benzenes are useful precursors in the synthesis of monodisperse aromatic oligomers (Lightowler & Hird, 2005 ). The tert-butoxy radicals plays an active role in initiating polymerization (Rizzardo & Solomon, 1979 ).

In the title compound (Fig. 1), the bromobutoxy side chains are attached to the benzene ring in positions 1 and 3. The asymmetric unit contains one-half of the molecule, the whole molecule being generated by twofold rotational symmetry. This twofold axis bisects the benzene ring at atoms C5 and C8. The dihedral angle between the benzene ring and the mean plane which best fits the atoms of the bromobutoxy side chain is 40.75°. The angle between the bonds [O1—C7 and C7a—O1a; symmetry code: (a) −x + 1, y, −z + $[{1\over 2}]$ ] connecting the bromobutoxy side chains with the benzene ring is 69.9 (2)°. In the crystal, molecules are linked by C—H⋯π interactions, forming chains along the a-axis direction (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the bezne ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯Cg1ⁱ	0.97	2.81	3.664 (4)	147
Symmetry code: (i) x-1, y, z.

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by the twofold rotation axis (symmetry code: −x + 1, y, −z + $[{1\over 2}]$ ) that bisects atoms C5 and C8.

Figure 2
The crystal packing of the title compound, viewed along the a axis.

Synthesis and crystallization

A mixture of resorcinol/hydroquinol (1.0 equivalent) and potassium carbonate (2.0 equivalents) in acetone (50 ml) was stirred for 15 min at 333 K. 1,3-Dibromobutane (2.1 equivalents) was added to the reaction mixture and stirred at 333 K for 7 h. After completion of the reaction (monitored by thin-layer chromatography), the solvent was removed under reduced pressure and the residue was extracted with CHCl₃ (3 × 100 ml), then washed with water (2 × 100 ml) and brine (150 ml), and finally dried over anhydrous Na₂SO₄. The resulting solution was filtered and concentrated in vacuo and the residue obtained was purified by column chromatography using CHCl₃–hexane (1:9 v/v) as eluent. The white solid obtained was crystallized from methanol solution by slow evaporation, giving colourless block-like crystals.

Refinement

Crystal 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	Orthorhombic, Pbcn
Temperature (K)	296
a, b, c (Å)	4.8948 (3), 11.4976 (8), 27.636 (2)
V (Å³)	1555.30 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.21
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.562, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	17085, 1366, 974
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.070, 1.08
No. of reflections	1366
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.39
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), SHELXL2016 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1570193

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314617012081/su4161sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012081/su4161Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617012081/su4161Isup3.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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

1,3-Bis(4-bromobutoxy)benzene top

Crystal data top

C₁₄H₂₀Br₂O₂	D_x = 1.623 Mg m⁻³
M_r = 380.12	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 4934 reflections
a = 4.8948 (3) Å	θ = 5.9–48.6°
b = 11.4976 (8) Å	µ = 5.21 mm⁻¹
c = 27.636 (2) Å	T = 296 K
V = 1555.30 (18) Å³	Block, colourless
Z = 4	0.35 × 0.30 × 0.25 mm
F(000) = 760

Data collection top

Bruker Kappa APEXII CCD diffractometer	974 reflections with I > 2σ(I)
Bruker axs kappa axes2 CCD Diffractometer scans	R_int = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 25.0°, θ_min = 3.0°
T_min = 0.562, T_max = 0.745	h = −5→5
17085 measured reflections	k = −13→13
1366 independent reflections	l = −32→27

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0142P)² + 2.6984P] where P = (F_o² + 2F_c²)/3
1366 reflections	(Δ/σ)_max < 0.001
83 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.39 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.

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

	x	y	z	U_iso*/U_eq
Br1	0.11607 (11)	0.33877 (4)	0.03546 (2)	0.0782 (2)
O1	0.1750 (5)	0.64764 (18)	0.18910 (8)	0.0444 (6)
C8	0.500000	0.6559 (4)	0.250000	0.0356 (10)
H8	0.499996	0.575059	0.250002	0.043*
C6	0.3314 (7)	0.8365 (3)	0.21849 (12)	0.0418 (8)
H6	0.218658	0.877424	0.197420	0.050*
C7	0.3318 (6)	0.7156 (3)	0.21855 (11)	0.0346 (7)
C3	−0.1534 (8)	0.6095 (3)	0.12858 (13)	0.0534 (10)
H3A	−0.288821	0.645044	0.107659	0.064*
H3B	−0.249217	0.560942	0.151726	0.064*
C5	0.500000	0.8946 (4)	0.250000	0.0457 (12)
H5	0.499996	0.975466	0.250001	0.055*
C4	−0.0030 (7)	0.7038 (3)	0.15550 (12)	0.0463 (9)
H4A	0.101479	0.751205	0.133121	0.056*
H4B	−0.131214	0.753551	0.172471	0.056*
C1	−0.1216 (9)	0.4392 (4)	0.07311 (15)	0.0707 (12)
H1A	−0.256633	0.473929	0.051861	0.085*
H1B	−0.217731	0.392901	0.096989	0.085*
C2	0.0331 (8)	0.5336 (3)	0.09825 (13)	0.0520 (10)
H2A	0.125154	0.581386	0.074360	0.062*
H2B	0.171316	0.499101	0.118904	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1073 (4)	0.0652 (3)	0.0622 (3)	0.0010 (3)	−0.0155 (3)	−0.0107 (2)
O1	0.0516 (15)	0.0376 (12)	0.0439 (12)	−0.0008 (12)	−0.0128 (11)	0.0034 (10)
C8	0.043 (3)	0.029 (2)	0.035 (2)	0.000	0.005 (2)	0.000
C6	0.045 (2)	0.0326 (16)	0.0474 (18)	0.0052 (18)	0.0027 (16)	0.0071 (16)
C7	0.0363 (19)	0.0331 (16)	0.0343 (16)	−0.0027 (15)	0.0045 (15)	0.0001 (14)
C3	0.045 (2)	0.066 (2)	0.050 (2)	0.001 (2)	−0.0093 (18)	0.0053 (19)
C5	0.046 (3)	0.029 (2)	0.061 (3)	0.000	0.002 (3)	0.000
C4	0.045 (2)	0.049 (2)	0.044 (2)	0.0043 (18)	−0.0043 (18)	0.0049 (17)
C1	0.076 (3)	0.068 (3)	0.068 (3)	−0.013 (3)	−0.007 (3)	−0.004 (2)
C2	0.057 (2)	0.055 (2)	0.044 (2)	−0.007 (2)	−0.0086 (19)	−0.0001 (18)

Geometric parameters (Å, º) top

Br1—C1	1.942 (4)	C3—H3A	0.9700
O1—C7	1.364 (4)	C3—H3B	0.9700
O1—C4	1.428 (4)	C5—H5	0.9300
C8—C7ⁱ	1.380 (4)	C4—H4A	0.9700
C8—C7	1.380 (4)	C4—H4B	0.9700
C8—H8	0.9300	C1—C2	1.494 (5)
C6—C5	1.373 (4)	C1—H1A	0.9700
C6—C7	1.390 (4)	C1—H1B	0.9700
C6—H6	0.9300	C2—H2A	0.9700
C3—C4	1.507 (5)	C2—H2B	0.9700
C3—C2	1.515 (5)

C7—O1—C4	118.2 (2)	O1—C4—C3	107.1 (3)
C7ⁱ—C8—C7	120.4 (4)	O1—C4—H4A	110.3
C7ⁱ—C8—H8	119.8	C3—C4—H4A	110.3
C7—C8—H8	119.8	O1—C4—H4B	110.3
C5—C6—C7	119.0 (3)	C3—C4—H4B	110.3
C5—C6—H6	120.5	H4A—C4—H4B	108.6
C7—C6—H6	120.5	C2—C1—Br1	112.2 (3)
O1—C7—C8	115.3 (3)	C2—C1—H1A	109.2
O1—C7—C6	124.8 (3)	Br1—C1—H1A	109.2
C8—C7—C6	119.9 (3)	C2—C1—H1B	109.2
C4—C3—C2	113.2 (3)	Br1—C1—H1B	109.2
C4—C3—H3A	108.9	H1A—C1—H1B	107.9
C2—C3—H3A	108.9	C1—C2—C3	111.7 (3)
C4—C3—H3B	108.9	C1—C2—H2A	109.3
C2—C3—H3B	108.9	C3—C2—H2A	109.3
H3A—C3—H3B	107.8	C1—C2—H2B	109.3
C6ⁱ—C5—C6	121.8 (4)	C3—C2—H2B	109.3
C6ⁱ—C5—H5	119.1	H2A—C2—H2B	107.9
C6—C5—H5	119.1

C4—O1—C7—C8	−179.7 (2)	C7—C6—C5—C6ⁱ	0.0 (2)
C4—O1—C7—C6	0.2 (5)	C7—O1—C4—C3	−179.0 (3)
C7ⁱ—C8—C7—O1	179.9 (3)	C2—C3—C4—O1	−64.1 (4)
C7ⁱ—C8—C7—C6	0.0 (2)	Br1—C1—C2—C3	−178.5 (2)
C5—C6—C7—O1	−179.9 (2)	C4—C3—C2—C1	178.5 (3)
C5—C6—C7—C8	0.0 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the bezne ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cg1ⁱⁱ	0.97	2.81	3.664 (4)	147

Symmetry code: (ii) x−1, y, z.

Acknowledgements

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

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