1-Bromo-2-(4-methoxy­phen­oxy)ethane

Shen, L.; Hu, Y.-H.; Yang, W.-G.; Zhao, X.-L.; Yao, J.-F.

doi:10.1107/S1600536810001893

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o439

https://doi.org/10.1107/S1600536810001893

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1-Bromo-2-(4-methoxyphenoxy)ethane

Lei Shen,^a Yong-Hong Hu,^b Wen-Ge Yang,^a ^* Xiao-Lei Zhao ^a and Jin-Feng Yao ^a

^aSchool of Pharmaceutical Sciences, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Life Science and Pharmaceutical Engineering, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: chemywg@126.com

(Received 14 December 2009; accepted 15 January 2010; online 23 January 2010)

In the crystal structure of the title compound, C₉H₁₁BrO₂, molecules are stacked parallel to the b-axis direction, forming double layers in which the molecules are arranged head-to-head, with the bromomethyl groups pointing towards each other.

Related literature

For background to the use of the title compound as a pharmaceutical intermediate, see: Ran et al. (2000 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₁₁BrO₂
M_r = 231.09
Monoclinic, P 2₁ /c
a = 21.112 (4) Å
b = 5.4180 (11) Å
c = 8.3230 (17) Å
β = 94.54 (3)°
V = 949.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.29 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.481, T_max = 0.674
1759 measured reflections
1713 independent reflections
1050 reflections with I > 2σ(I)
R_int = 0.073
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.155
S = 1.01
1713 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810001893/jh2122sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001893/jh2122Isup2.hkl

checkCIF report

Comment top

The tile compound, (I), contains halogen and methoxy groups, which can react with differen groups to prepare various functional organic compounds as a fine organic intermediate (Ran et al., 2000). we report herein its crystal structure.

In the molecule of the tile compound (Fig.1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The O1 and O2 atoms (Table 1) lie in the benzene ring plane. No intramolecular hydrogen bonds were observed.

In the crystal structure, the molecules are stacked along the b axis and the 'double layers' of molecules lying with all their bromomethyl groups together (Fig.2).

Related literature top

For background to the use of the title compound as a pharmaceutical intermediate, see: Ran et al. (2000). For bond-length data, see: Allen et al. (1987).

Experimental top

4-methoxyphenol (18.6 g,0.15 mol) was dissolved with stirring in water (80 ml) containing sodium hydroxide (9.0 g, 0.25 mol) and TBAB (0.48 g, 0.0015 mol) and then added dropwise to excess refluxing ethylene dibromide (65 g, 0.35 mol). The reaction mixture was heated under reflux for 12 h, cooled and extracted into chloroform. The combined organic extracts were washed with water, dried over Na₂SO₄, filtered and evaporated to dryness to yield an oil. Fractionation under reduced pressure yielded 1-Bromo-2-(4-methoxyphenoxy)ethane as a colorless oil, then cooled to give 27.3 g white solid (78.9% yield). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.

Structure description top

In the crystal structure, the molecules are stacked along the b axis and the 'double layers' of molecules lying with all their bromomethyl groups together (Fig.2).

For background to the use of the title compound as a pharmaceutical intermediate, see: Ran et al. (2000). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I).

1-Bromo-2-(4-methoxyphenoxy)ethane top

Crystal data top

C₉H₁₁BrO₂	F(000) = 464
M_r = 231.09	D_x = 1.617 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 21.112 (4) Å	θ = 9–13°
b = 5.4180 (11) Å	µ = 4.29 mm⁻¹
c = 8.3230 (17) Å	T = 293 K
β = 94.54 (3)°	Block, colourless
V = 949.0 (3) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1050 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.073
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = −25→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.481, T_max = 0.674	l = −9→9
1759 measured reflections	3 standard reflections every 200 reflections
1713 independent reflections	intensity decay: 1%

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)] = 0.069	H-atom parameters constrained
wR(F²) = 0.155	w = 1/[σ²(F_o²) + (0.060P)² + 5.P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1713 reflections	Δρ_max = 0.66 e Å⁻³
110 parameters	Δρ_min = −0.55 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: 0.010 (2)

Crystal data top

C₉H₁₁BrO₂	V = 949.0 (3) Å³
M_r = 231.09	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 21.112 (4) Å	µ = 4.29 mm⁻¹
b = 5.4180 (11) Å	T = 293 K
c = 8.3230 (17) Å	0.20 × 0.10 × 0.10 mm
β = 94.54 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1050 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.073
T_min = 0.481, T_max = 0.674	3 standard reflections every 200 reflections
1759 measured reflections	intensity decay: 1%
1713 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.01	Δρ_max = 0.66 e Å⁻³
1713 reflections	Δρ_min = −0.55 e Å⁻³
110 parameters

Special details top

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
Br	0.43028 (5)	0.39656 (16)	0.68335 (11)	0.0565 (4)
O1	0.0725 (3)	0.4636 (12)	0.1822 (7)	0.0603 (17)
C1	0.0493 (5)	0.2506 (19)	0.0971 (11)	0.068 (3)
H1A	0.0047	0.2689	0.0682	0.102*
H1B	0.0564	0.1077	0.1643	0.102*
H1C	0.0713	0.2313	0.0012	0.102*
O2	0.3246 (3)	0.5406 (10)	0.4019 (5)	0.0443 (14)
C2	0.1538 (4)	0.6649 (13)	0.3366 (8)	0.0344 (18)
H2A	0.1238	0.7785	0.3664	0.041*
C3	0.1353 (3)	0.4740 (14)	0.2328 (8)	0.0305 (17)
C4	0.2150 (3)	0.6877 (13)	0.3951 (8)	0.0317 (17)
H4A	0.2263	0.8141	0.4673	0.038*
C5	0.2602 (3)	0.5311 (12)	0.3510 (7)	0.0266 (16)
C6	0.2427 (4)	0.3359 (14)	0.2494 (8)	0.0374 (19)
H6A	0.2731	0.2239	0.2203	0.045*
C7	0.1801 (4)	0.3076 (14)	0.1914 (8)	0.0361 (19)
H7A	0.1683	0.1755	0.1243	0.043*
C8	0.3458 (4)	0.7249 (14)	0.5127 (8)	0.039 (2)
H8A	0.3222	0.7152	0.6079	0.047*
H8B	0.3387	0.8866	0.4646	0.047*
C9	0.4136 (4)	0.6893 (15)	0.5575 (9)	0.0408 (19)
H9A	0.4299	0.8313	0.6186	0.049*
H9B	0.4360	0.6791	0.4603	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0742 (7)	0.0413 (5)	0.0505 (6)	0.0066 (5)	−0.0173 (4)	0.0053 (5)
O1	0.051 (4)	0.066 (4)	0.062 (4)	0.002 (3)	−0.011 (3)	−0.013 (3)
C1	0.076 (7)	0.069 (7)	0.056 (6)	−0.010 (6)	−0.021 (5)	−0.011 (5)
O2	0.061 (4)	0.051 (4)	0.019 (3)	0.002 (3)	−0.006 (2)	−0.007 (2)
C2	0.053 (5)	0.026 (4)	0.025 (4)	0.006 (3)	0.006 (3)	0.005 (3)
C3	0.036 (4)	0.037 (4)	0.018 (4)	0.008 (4)	0.000 (3)	−0.007 (3)
C4	0.045 (4)	0.022 (4)	0.027 (4)	0.002 (4)	0.001 (3)	−0.009 (3)
C5	0.046 (4)	0.023 (4)	0.010 (3)	0.002 (3)	−0.001 (3)	0.005 (3)
C6	0.058 (5)	0.033 (5)	0.020 (4)	0.004 (4)	−0.003 (3)	0.000 (3)
C7	0.064 (5)	0.026 (4)	0.016 (4)	−0.001 (4)	−0.011 (3)	−0.003 (3)
C8	0.068 (6)	0.029 (4)	0.018 (4)	−0.011 (4)	−0.008 (3)	0.005 (3)
C9	0.048 (5)	0.040 (5)	0.034 (4)	−0.016 (4)	0.000 (4)	0.004 (4)

Geometric parameters (Å, º) top

Br—C9	1.918 (8)	C4—C5	1.350 (9)
O1—C3	1.360 (9)	C4—H4A	0.9300
O1—C1	1.421 (11)	C5—C6	1.386 (9)
C1—H1A	0.9600	C6—C7	1.380 (10)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C7—H7A	0.9300
O2—C5	1.393 (8)	C8—C9	1.463 (10)
O2—C8	1.408 (9)	C8—H8A	0.9700
C2—C4	1.350 (10)	C8—H8B	0.9700
C2—C3	1.384 (10)	C9—H9A	0.9700
C2—H2A	0.9300	C9—H9B	0.9700
C3—C7	1.370 (10)

C3—O1—C1	118.4 (7)	C6—C5—O2	114.9 (6)
O1—C1—H1A	109.5	C7—C6—C5	120.0 (7)
O1—C1—H1B	109.5	C7—C6—H6A	120.0
H1A—C1—H1B	109.5	C5—C6—H6A	120.0
O1—C1—H1C	109.5	C3—C7—C6	120.0 (7)
H1A—C1—H1C	109.5	C3—C7—H7A	120.0
H1B—C1—H1C	109.5	C6—C7—H7A	120.0
C5—O2—C8	118.5 (6)	O2—C8—C9	109.1 (7)
C4—C2—C3	120.6 (7)	O2—C8—H8A	109.9
C4—C2—H2A	119.7	C9—C8—H8A	109.9
C3—C2—H2A	119.7	O2—C8—H8B	109.9
O1—C3—C7	124.8 (6)	C9—C8—H8B	109.9
O1—C3—C2	116.4 (6)	H8A—C8—H8B	108.3
C7—C3—C2	118.8 (7)	C8—C9—Br	112.4 (5)
C2—C4—C5	121.5 (7)	C8—C9—H9A	109.1
C2—C4—H4A	119.3	Br—C9—H9A	109.1
C5—C4—H4A	119.3	C8—C9—H9B	109.1
C4—C5—C6	119.0 (7)	Br—C9—H9B	109.1
C4—C5—O2	126.1 (6)	H9A—C9—H9B	107.9

C1—O1—C3—C7	8.3 (11)	C8—O2—C5—C6	−176.4 (6)
C1—O1—C3—C2	−170.1 (7)	C4—C5—C6—C7	1.7 (10)
C4—C2—C3—O1	179.0 (7)	O2—C5—C6—C7	179.9 (6)
C4—C2—C3—C7	0.5 (10)	O1—C3—C7—C6	179.8 (7)
C3—C2—C4—C5	2.0 (11)	C2—C3—C7—C6	−1.8 (10)
C2—C4—C5—C6	−3.1 (10)	C5—C6—C7—C3	0.7 (10)
C2—C4—C5—O2	178.9 (6)	C5—O2—C8—C9	176.1 (6)
C8—O2—C5—C4	1.6 (9)	O2—C8—C9—Br	−68.6 (7)

Experimental details

Crystal data
Chemical formula	C₉H₁₁BrO₂
M_r	231.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	21.112 (4), 5.4180 (11), 8.3230 (17)
β (°)	94.54 (3)
V (Å³)	949.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.29
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.481, 0.674
No. of measured, independent and observed [I > 2σ(I)] reflections	1759, 1713, 1050
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.155, 1.01
No. of reflections	1713
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.55

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Br—C9	1.918 (8)	O2—C5	1.393 (8)
O1—C3	1.360 (9)	O2—C8	1.408 (9)
O1—C1	1.421 (11)

C3—O1—C1	118.4 (7)	C4—C5—O2	126.1 (6)
C5—O2—C8	118.5 (6)	C6—C5—O2	114.9 (6)
O1—C3—C7	124.8 (6)	O2—C8—C9	109.1 (7)
O1—C3—C2	116.4 (6)	C8—C9—Br	112.4 (5)

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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