Bis(2-bromo­benz­yl) ether

Anuradha, V.; Nagendra, P.; Madan Kumar, S.; Siddaraju, B.P.; Lokanath, N.K.

doi:10.1107/S1600536814011738

organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page o765

https://doi.org/10.1107/S1600536814011738

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Bis(2-bromobenzyl) ether

Venkatramu Anuradha,^a P. Nagendra,^b S. Madan Kumar,^c B. P. Siddaraju ^d and N. K. Lokanath ^c ^*

^aDepartment of Physics, Dr M. G. R. Educational and Research Institute, Maduravoyal, Chennai, India, ^bDepartment of Chemistry, BET Academy of Higher Education, Bharathi College, Bharthi Nagara, Mandya 571 422, India, ^cDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^dDepartment of Chemistry, G. Made Gowda Institute of Technology, Bharthi Nagara, Mandya 571422, India
^*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

(Received 12 May 2014; accepted 21 May 2014; online 11 June 2014)

In the title compound, C₁₄H₁₂Br₂O, the dihedral angle between the aromatic rings is 2.7 (3)° and the Br atoms lie on the same side of the molecule. No intermolecular interactions occur in the crystal beyond van der Waals contacts.

CCDC reference: 1004401

Related literature

For the use of benzyl groups in organic synthesis, see; Rao & Kumar (2001 ); Tareque et al. (2006 ).

Experimental

Crystal data

C₁₄H₁₂Br₂O
M_r = 356.04
Monoclinic, P 2₁ /n
a = 11.6022 (6) Å
b = 10.1590 (5) Å
c = 12.2368 (6) Å
β = 112.853 (2)°
V = 1329.10 (12) Å³
Z = 4
Cu Kα radiation
μ = 7.58 mm⁻¹
T = 296 K
0.23 × 0.22 × 0.21 mm

Data collection

Bruker X8 Proteum diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013) T_min = 0.275, T_max = 0.299
10361 measured reflections
2185 independent reflections
1957 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.192
S = 1.07
2185 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 1.26 e Å⁻³
Δρ_min = −1.61 e Å⁻³

Data collection: APEX2 (Bruker, 2013 ); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: Mercury.

Supporting information

CCDC reference: 1004401

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536814011738/hb7230sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814011738/hb7230Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814011738/hb7230Isup3.cml

checkCIF report

Comment top

Benzyl groups are commonly used for the protection of alcohol and phenol moieties for synthesis. The benzyl alcohol used in the benzylation of phenol (Tareque, et al.,, 2006). The benzyl ethers are used as intermediates in sigmatropic rearrangement reactions such as Claisen and the Cope rearrangements (Rao and Kumar, 2001).

In the title compound, C₁₄H₁₀Br₂O, (Fig. 1), the dihedral angle between the aromatic rings is 2.7 (3)° and the Br atoms lie on the same side of the molecule. No intermolecular interactions occur in the crystal beyond van der Waals' contacts.

Related literature top

For the use of benzyl groups in organic synthesis, see; Rao & Kumar (2001); Tareque et al. (2006).

Experimental top

2-Bromobenzyl alcohol (1.87 g, 0.01 mol), sodium hydride 0.24 g, 0.01 mol) and 2-bromobenzyl bromide (2.52 g, 0.01 mol) were ground well and mixed in 25 ml of THF. The mixture were stirred in a beaker at 60 °C for one hour. The mixture was kept aside for five days at room temperature in a vaccum desiccator over phosphorous pentoxide. The colourless crystals were obtained by slow evaporation (M. P. 374 - 376 K). Colourless blocks were obtained from slow evaporation of a solution of ethylacetate.

Structure description top

For the use of benzyl groups in organic synthesis, see; Rao & Kumar (2001); Tareque et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008).

Figures top

	Fig. 1. A view of the title molecule, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A viewed along the b axis of the crystal packing of the title compound.

Bis(2-bromobenzyl) ether top

Crystal data top

C₁₄H₁₂Br₂O	F(000) = 688
M_r = 356.04	D_x = 1.769 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 2185 reflections
a = 11.6022 (6) Å	θ = 4.5–64.7°
b = 10.1590 (5) Å	µ = 7.58 mm⁻¹
c = 12.2368 (6) Å	T = 296 K
β = 112.853 (2)°	Block, colourless
V = 1329.10 (12) Å³	0.23 × 0.22 × 0.21 mm
Z = 4

Data collection top

Bruker X8 Proteum diffractometer	2185 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1957 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.054
Detector resolution: 10.7 pixels mm^-1	θ_max = 64.7°, θ_min = 4.5°
φ and ω scans	h = −5→13
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −11→11
T_min = 0.275, T_max = 0.299	l = −14→11
10361 measured reflections

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)] = 0.073	H-atom parameters constrained
wR(F²) = 0.192	w = 1/[σ²(F_o²) + (0.137P)² + 1.9645P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2185 reflections	Δρ_max = 1.26 e Å⁻³
155 parameters	Δρ_min = −1.61 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: 0.0219 (17)

Crystal data top

C₁₄H₁₂Br₂O	V = 1329.10 (12) Å³
M_r = 356.04	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.6022 (6) Å	µ = 7.58 mm⁻¹
b = 10.1590 (5) Å	T = 296 K
c = 12.2368 (6) Å	0.23 × 0.22 × 0.21 mm
β = 112.853 (2)°

Data collection top

Bruker X8 Proteum diffractometer	2185 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	1957 reflections with I > 2σ(I)
T_min = 0.275, T_max = 0.299	R_int = 0.054
10361 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.192	H-atom parameters constrained
S = 1.07	Δρ_max = 1.26 e Å⁻³
2185 reflections	Δρ_min = −1.61 e Å⁻³
155 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2sigma(F²) is used only for calculating -R-factor-obs 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	0.45265 (7)	0.18786 (6)	0.48911 (7)	0.0610 (3)
Br2	1.11871 (7)	0.50492 (7)	0.78422 (6)	0.0629 (4)
O1	0.7350 (4)	0.4954 (4)	0.4857 (4)	0.0441 (14)
C1	1.0514 (5)	0.6241 (6)	0.6552 (5)	0.0410 (17)
C2	1.1258 (5)	0.7260 (7)	0.6461 (6)	0.051 (2)
C3	1.0785 (6)	0.8126 (6)	0.5532 (6)	0.052 (2)
C4	0.9584 (6)	0.7975 (6)	0.4701 (6)	0.0488 (19)
C5	0.8845 (5)	0.6954 (5)	0.4814 (5)	0.0391 (17)
C6	0.9296 (5)	0.6058 (5)	0.5729 (5)	0.0348 (16)
C7	0.8506 (5)	0.4919 (5)	0.5835 (5)	0.0389 (17)
C8	0.6547 (5)	0.3941 (5)	0.4916 (5)	0.0384 (16)
C9	0.5324 (5)	0.4041 (5)	0.3857 (5)	0.0350 (16)
C10	0.5112 (5)	0.5001 (5)	0.3003 (5)	0.0411 (17)
C11	0.3985 (6)	0.5106 (7)	0.2048 (6)	0.053 (2)
C12	0.3028 (6)	0.4217 (6)	0.1926 (5)	0.0499 (17)
C13	0.3212 (6)	0.3256 (6)	0.2769 (6)	0.0493 (19)
C14	0.4339 (5)	0.3178 (5)	0.3721 (5)	0.0401 (16)
H2	1.20690	0.73590	0.70220	0.0610*
H3	1.12770	0.88170	0.54620	0.0630*
H4	0.92700	0.85570	0.40670	0.0590*
H5	0.80290	0.68710	0.42610	0.0460*
H7A	0.89290	0.40930	0.58440	0.0470*
H7B	0.83730	0.49890	0.65680	0.0470*
H8A	0.64000	0.40210	0.56410	0.0460*
H8B	0.69290	0.30910	0.49190	0.0460*
H10	0.57470	0.55950	0.30740	0.0490*
H11	0.38640	0.57660	0.14880	0.0630*
H12	0.22690	0.42740	0.12790	0.0600*
H13	0.25770	0.26610	0.26950	0.0590*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0563 (6)	0.0420 (5)	0.0818 (7)	−0.0090 (3)	0.0236 (4)	0.0184 (3)
Br2	0.0562 (6)	0.0755 (7)	0.0436 (6)	0.0143 (3)	0.0047 (4)	−0.0006 (3)
O1	0.031 (2)	0.047 (2)	0.054 (3)	−0.0052 (16)	0.0161 (18)	0.0079 (16)
C1	0.039 (3)	0.048 (3)	0.038 (3)	0.004 (2)	0.017 (2)	−0.014 (2)
C2	0.035 (3)	0.058 (4)	0.058 (4)	−0.009 (3)	0.015 (3)	−0.025 (3)
C3	0.046 (3)	0.047 (4)	0.068 (4)	−0.014 (3)	0.028 (3)	−0.016 (3)
C4	0.048 (3)	0.039 (3)	0.061 (4)	−0.003 (2)	0.023 (3)	−0.004 (3)
C5	0.033 (3)	0.037 (3)	0.046 (3)	0.002 (2)	0.014 (2)	−0.004 (2)
C6	0.031 (2)	0.037 (3)	0.041 (3)	0.0037 (19)	0.019 (2)	−0.011 (2)
C7	0.034 (3)	0.043 (3)	0.041 (3)	0.003 (2)	0.016 (2)	0.002 (2)
C8	0.030 (2)	0.037 (3)	0.052 (3)	−0.001 (2)	0.020 (2)	0.007 (2)
C9	0.033 (2)	0.033 (3)	0.046 (3)	0.004 (2)	0.023 (2)	−0.002 (2)
C10	0.042 (3)	0.043 (3)	0.044 (3)	−0.003 (2)	0.023 (3)	0.005 (2)
C11	0.048 (4)	0.062 (4)	0.052 (4)	0.008 (3)	0.023 (3)	0.011 (3)
C12	0.040 (3)	0.056 (3)	0.049 (3)	0.003 (3)	0.012 (2)	−0.002 (3)
C13	0.039 (3)	0.045 (3)	0.064 (4)	−0.008 (2)	0.020 (3)	−0.013 (3)
C14	0.037 (3)	0.029 (2)	0.060 (3)	−0.0028 (19)	0.025 (3)	−0.004 (2)

Geometric parameters (Å, º) top

Br1—C14	1.897 (5)	C11—C12	1.394 (10)
Br2—C1	1.900 (6)	C12—C13	1.375 (9)
O1—C7	1.409 (8)	C13—C14	1.375 (9)
O1—C8	1.409 (7)	C2—H2	0.9300
C1—C2	1.380 (9)	C3—H3	0.9300
C1—C6	1.393 (8)	C4—H4	0.9300
C2—C3	1.372 (9)	C5—H5	0.9300
C3—C4	1.378 (10)	C7—H7A	0.9700
C4—C5	1.386 (9)	C7—H7B	0.9700
C5—C6	1.379 (8)	C8—H8A	0.9700
C6—C7	1.513 (8)	C8—H8B	0.9700
C8—C9	1.508 (8)	C10—H10	0.9300
C9—C10	1.380 (8)	C11—H11	0.9300
C9—C14	1.398 (8)	C12—H12	0.9300
C10—C11	1.378 (9)	C13—H13	0.9300

C7—O1—C8	111.6 (4)	C2—C3—H3	120.00
Br2—C1—C2	118.5 (5)	C4—C3—H3	120.00
Br2—C1—C6	119.3 (4)	C3—C4—H4	120.00
C2—C1—C6	122.2 (6)	C5—C4—H4	120.00
C1—C2—C3	119.1 (6)	C4—C5—H5	119.00
C2—C3—C4	120.3 (6)	C6—C5—H5	119.00
C3—C4—C5	119.8 (6)	O1—C7—H7A	110.00
C4—C5—C6	121.4 (6)	O1—C7—H7B	110.00
C1—C6—C5	117.2 (5)	C6—C7—H7A	110.00
C1—C6—C7	121.2 (5)	C6—C7—H7B	110.00
C5—C6—C7	121.5 (5)	H7A—C7—H7B	108.00
O1—C7—C6	108.5 (4)	O1—C8—H8A	110.00
O1—C8—C9	109.1 (4)	O1—C8—H8B	110.00
C8—C9—C10	122.0 (5)	C9—C8—H8A	110.00
C8—C9—C14	120.9 (5)	C9—C8—H8B	110.00
C10—C9—C14	117.1 (5)	H8A—C8—H8B	108.00
C9—C10—C11	121.9 (6)	C9—C10—H10	119.00
C10—C11—C12	119.7 (6)	C11—C10—H10	119.00
C11—C12—C13	119.6 (6)	C10—C11—H11	120.00
C12—C13—C14	119.7 (6)	C12—C11—H11	120.00
Br1—C14—C9	119.9 (4)	C11—C12—H12	120.00
Br1—C14—C13	118.2 (5)	C13—C12—H12	120.00
C9—C14—C13	122.0 (5)	C12—C13—H13	120.00
C1—C2—H2	120.00	C14—C13—H13	120.00
C3—C2—H2	120.00

C8—O1—C7—C6	−178.2 (5)	C5—C6—C7—O1	2.3 (7)
C7—O1—C8—C9	179.3 (5)	O1—C8—C9—C10	0.5 (7)
Br2—C1—C2—C3	179.8 (5)	O1—C8—C9—C14	−177.6 (5)
C6—C1—C2—C3	0.2 (10)	C8—C9—C10—C11	−178.7 (6)
Br2—C1—C6—C5	179.5 (4)	C14—C9—C10—C11	−0.6 (9)
Br2—C1—C6—C7	−0.8 (8)	C8—C9—C14—Br1	1.0 (7)
C2—C1—C6—C5	−0.9 (9)	C8—C9—C14—C13	179.5 (6)
C2—C1—C6—C7	178.9 (6)	C10—C9—C14—Br1	−177.2 (4)
C1—C2—C3—C4	−0.2 (10)	C10—C9—C14—C13	1.3 (9)
C2—C3—C4—C5	0.9 (10)	C9—C10—C11—C12	−0.5 (10)
C3—C4—C5—C6	−1.7 (10)	C10—C11—C12—C13	0.9 (10)
C4—C5—C6—C1	1.6 (9)	C11—C12—C13—C14	−0.3 (10)
C4—C5—C6—C7	−178.2 (6)	C12—C13—C14—Br1	177.7 (5)
C1—C6—C7—O1	−177.4 (5)	C12—C13—C14—C9	−0.9 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1	0.93	2.32	2.685 (7)	103
C10—H10···O1	0.93	2.34	2.705 (8)	103

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1	0.9300	2.3200	2.685 (7)	103.00
C10—H10···O1	0.9300	2.3400	2.705 (8)	103.00

Acknowledgements

We are grateful to the IOE, University of Mysore, for providing the single-crystal X-ray diffraction facility. PN thanks the BET Academy of Higher Education for the facilities.

References

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