Bis(2-bromo-5-methyl­phen­­oxy)methane

The complete mol­ecule of the title compund, C₁₅H₁₄Br₂O₂, is generated by the application of crystallographic twofold symmetry, with the central C atom lying on the rotation axis. The dihedral angle between the benzene rings is 62.4 (3)°. In the crystal, short Br⋯Br contacts [3.4885 (16) Å] occur.

Related literature

For background to bromo­aromatic compounds, see: Butler & Walker (1993); Seevers & Counsell (1982). For a related structure, see: Zheng et al. (2004).

Experimental

Crystal data

• C₁₅H₁₄Br₂O₂

• M_r = 386.08

• Orthorhombic, P 2₁ 2₁ 2

• a = 10.7752 (11) Å

• b = 15.8690 (17) Å

• c = 4.3272 (10) Å

• V = 739.9 (2) ų

• Z = 2

• Cu Kα radiation

• μ = 6.91 mm⁻¹

• T = 291 K

• 0.35 × 0.30 × 0.30 mm

Data collection

• Agilent Xcalibur Eos Gemini diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) T_min = 0.196, T_max = 0.231

• 1505 measured reflections

• 1022 independent reflections

• 754 reflections with I > 2σ(I)

• R_int = 0.044

Refinement

• R[F² > 2σ(F²)] = 0.055

• wR(F²) = 0.123

• S = 1.02

• 1022 reflections

• 88 parameters

• H-atom parameters constrained

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

• Absolute structure: Flack (1983), 212 Friedel pairs

• Flack parameter: −0.11 (9)

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

Bromoaromatic compounds have proven to be an important class of molecules in synthetic organic chemistry. They have been used as key intermediates in the preparation of oganometallic reagents and play vital roles in transition metal mediated coupling reactions (Butler et al., 1993; Seevers et al., 1982). In this paper, we synthesized the title compound and reported its crystal structure here. The title compound was synthesized by the reaction of 2-bromo-4-methylphenol, dibromomethane with potassium carbonate. The C—C—C angles within the aromatic moiety cover a range 117.7 (8) - 122.5 (8) °, and the two benzene rings make a dihedral angle of 62.5° (Fig. 1). The O and Br atoms are essentially coplanar with the benzene ring to which they are attached, with the deviation of 0.0074 Å. In addition, the benzene rings between the adjacent molecules are stacked in a face-to-face orientation with the distance of 3.701 Å, a distance longer than the π–π stacking distances of 3.33 - 3.53 Å reported elsewhere (Zheng et al., 2004), indicating no π–π stacking is observed for this compound.

Related literature

For background to bromoaromatic compounds, see: Butler & Walker (1993); Seevers & Counsell (1982). For a related structure, see: Zheng et al. (2004).

S2. Experimental

A mixture of 2-bromo-4-methylphenol (188 mg, 1 mmol), potassium carbonate (691 mg, 5 mmol) and dibromomethane (0.75 mmol) in acetone (5 ml) was heated to reflux for 12 h. The product was isolated and recrystallized from dicholomethane/hexane, colorless prisms of the title compound were obtained.

S3. Refinement

H atoms were generated geometrically and refined as riding atoms with C-H = 0.93Å and Uiso(H) = 1.2 times Ueq(C).

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. View of the title compound, showing 30% probability ellipsolids. Atoms with suffix A are generated by (1–x, 2–y, z0.
	Fig. 2. A view of the crystal packing along the c axis, with short Br···Br contacts indicated by dashed lines.

Bis(2-bromo-5-methylphenoxy)methane

Crystal data

C15H14Br2O2	Dx = 1.733 Mg m^−3
Mr = 386.08	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P21212	Cell parameters from 443 reflections
a = 10.7752 (11) Å	θ = 4.1–69.9°
b = 15.8690 (17) Å	µ = 6.91 mm^−1
c = 4.3272 (10) Å	T = 291 K
V = 739.9 (2) Å^3	Prism, colorless
Z = 2	0.35 × 0.30 × 0.30 mm
F(000) = 380

Data collection

Agilent Xcalibur Eos Gemini diffractometer	1022 independent reflections
Radiation source: fine-focus sealed tube	754 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 16.2312 pixels mm^-1	θmax = 66.9°, θmin = 5.0°
ω scans	h = −12→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −18→14
Tmin = 0.196, Tmax = 0.231	l = −3→4
1505 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.040P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
1022 reflections	Δρmax = 0.36 e Å^−3
88 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Absolute structure: Flack (1983), 212 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.11 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.85154 (9)	0.95619 (6)	0.6233 (4)	0.0946 (6)
O1	0.6042 (5)	0.9803 (3)	0.3521 (17)	0.0668 (18)
C1	0.7175 (7)	0.8802 (4)	0.624 (3)	0.054 (2)
C2	0.6083 (7)	0.9029 (5)	0.489 (2)	0.056 (3)
C3	0.5091 (8)	0.8444 (5)	0.500 (2)	0.066 (3)
H3	0.4330	0.8573	0.4098	0.079*
C4	0.5267 (8)	0.7679 (5)	0.646 (3)	0.070 (3)
H4	0.4617	0.7294	0.6501	0.084*
C5	0.6369 (8)	0.7465 (4)	0.787 (2)	0.060 (3)
C6	0.7312 (8)	0.8044 (5)	0.779 (2)	0.058 (3)
H6	0.8056	0.7925	0.8792	0.069*
C7	0.6509 (9)	0.6621 (5)	0.946 (2)	0.090 (3)
H7A	0.7023	0.6684	1.1261	0.135*
H7B	0.6886	0.6226	0.8070	0.135*
H7C	0.5706	0.6417	1.0072	0.135*
C8	0.5000	1.0000	0.168 (4)	0.080 (5)
H8A	0.4805	0.9524	0.0361	0.096*	0.50
H8B	0.5195	1.0476	0.0361	0.096*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0546 (6)	0.0668 (6)	0.1623 (14)	−0.0129 (5)	−0.0131 (8)	0.0130 (8)
O1	0.049 (3)	0.062 (3)	0.089 (5)	0.017 (3)	0.004 (4)	0.012 (4)
C1	0.052 (4)	0.042 (4)	0.066 (7)	0.009 (3)	0.001 (5)	0.004 (5)
C2	0.048 (4)	0.056 (5)	0.062 (8)	0.020 (4)	0.010 (5)	−0.001 (5)
C3	0.043 (4)	0.081 (6)	0.074 (8)	0.006 (5)	−0.009 (5)	−0.012 (6)
C4	0.058 (5)	0.061 (5)	0.090 (9)	−0.011 (4)	0.009 (7)	−0.008 (7)
C5	0.064 (5)	0.041 (4)	0.074 (8)	−0.006 (4)	0.020 (5)	−0.001 (5)
C6	0.058 (5)	0.057 (5)	0.058 (7)	0.008 (4)	0.007 (5)	0.002 (5)
C7	0.110 (8)	0.062 (5)	0.098 (9)	−0.002 (6)	0.019 (9)	0.026 (6)
C8	0.082 (10)	0.077 (9)	0.081 (12)	0.023 (8)	0.000	0.000

Geometric parameters (Å, º)

Br1—C1	1.882 (7)	C5—C6	1.370 (10)
O1—C2	1.364 (9)	C5—C7	1.515 (10)
O1—C8	1.412 (10)	C6—H6	0.9300
C1—C2	1.363 (11)	C7—H7A	0.9600
C1—C6	1.385 (10)	C7—H7B	0.9600
C2—C3	1.417 (11)	C7—H7C	0.9600
C3—C4	1.383 (11)	C8—O1^i	1.412 (10)
C3—H3	0.9300	C8—H8A	0.9700
C4—C5	1.376 (12)	C8—H8B	0.9700
C4—H4	0.9300
C2—O1—C8	118.0 (6)	C5—C6—C1	121.0 (8)
C2—C1—C6	122.1 (7)	C5—C6—H6	119.5
C2—C1—Br1	119.4 (6)	C1—C6—H6	119.5
C6—C1—Br1	118.4 (6)	C5—C7—H7A	109.5
C1—C2—O1	117.0 (7)	C5—C7—H7B	109.5
C1—C2—C3	117.6 (8)	H7A—C7—H7B	109.5
O1—C2—C3	125.5 (8)	C5—C7—H7C	109.5
C4—C3—C2	119.2 (8)	H7A—C7—H7C	109.5
C4—C3—H3	120.4	H7B—C7—H7C	109.5
C2—C3—H3	120.4	O1—C8—O1^i	111.2 (12)
C5—C4—C3	122.5 (8)	O1—C8—H8A	109.4
C5—C4—H4	118.7	O1^i—C8—H8A	109.4
C3—C4—H4	118.7	O1—C8—H8B	109.4
C6—C5—C4	117.6 (8)	O1^i—C8—H8B	109.4
C6—C5—C7	122.0 (9)	H8A—C8—H8B	108.0
C4—C5—C7	120.3 (8)
C6—C1—C2—O1	177.7 (8)	C2—C3—C4—C5	1.0 (16)
Br1—C1—C2—O1	1.3 (13)	C3—C4—C5—C6	0.2 (16)
C6—C1—C2—C3	−2.4 (15)	C3—C4—C5—C7	179.6 (9)
Br1—C1—C2—C3	−178.8 (7)	C4—C5—C6—C1	−2.5 (15)
C8—O1—C2—C1	170.0 (9)	C7—C5—C6—C1	178.1 (8)
C8—O1—C2—C3	−9.8 (14)	C2—C1—C6—C5	3.7 (15)
C1—C2—C3—C4	0.1 (15)	Br1—C1—C6—C5	−179.8 (7)
O1—C2—C3—C4	179.9 (9)	C2—O1—C8—O1^i	76.7 (6)

Symmetry code: (i) −x+1, −y+2, z.