1-(3-Bromopropoxy)-4-chlorobenzene

Yang, W.; Yao, J.; Zhao, X.; Hu, Y.

doi:10.1107/S1600536808037896

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2422

doi:10.1107/S1600536808037896

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1-(3-Bromopropoxy)-4-chlorobenzene

Wen-ge Yang,^a ^* Jin-feng Yao,^a Xiao-lei Zhao ^a and Yong-hong Hu ^a

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

(Received 10 November 2008; accepted 14 November 2008; online 22 November 2008)

In the molecule of the title compound, C₈H₈BrClO, the Cl atom lies slightly out of the aromatic ring plane [displacement = 0.072 (3) Å]. In the crystal structure, a π–π contact between the phenyl rings [centroid–centroid distance = 3.699 (3) Å] may stabilize the structure. There also exists a C—H⋯π contact between the methylene group and the chlorophenyl ring.

Related literature

For general background, see: Zirngibl et al. (1988 ). For related structures, see: Menini & Gusevskaya (2006 ); Baggaley & Watts (1982 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₈BrClO
M_r = 235.50
Monoclinic, P 2₁ /c
a = 9.0680 (18) Å
b = 9.781 (2) Å
c = 10.238 (2) Å
β = 98.01 (3)°
V = 899.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.81 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf-Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.327, T_max = 0.382
1726 measured reflections
1620 independent reflections
769 reflections with I > 2σ(I)
R_int = 0.060
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.166
S = 1.00
1620 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Cg1ⁱ	0.97	2.88	3.665 (3)	138
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the C3–C8 ring.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); 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, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks Y, I. DOI: 10.1107/S1600536808037896/hk2572sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808037896/hk2572Isup2.hkl

checkCIF report

Comment top

Omoconazole has a high antifungal activity and a broad spectrum (Zirngibl et al., 1988). As part of our ongoing studies in this area, we report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C3-C8) is, of course, planar, and the Cl atom lies slightly out of the ring plane [0.072 (3) Å]. The (O1/C1/C2) and (Br/C1/C2) moieties are oriented with respect to ring A at dihedral angles of 11.57 (3)° and 74.97 (3)°, respectively.

In the crystal structure, the π-π contact between the phenyl rings, Cg1—Cg1ⁱ [symmetry code: (i) -x, 1 - y, -z, where Cg1 is centroid of the ring A (C3-C8)] may stabilize the structure, with centroid-centroid distance of 3.699 (3) Å. There also exists a C—H···π contact (Table 1) between the methylene group and the chlorophenyl ring.

Related literature top

For general background, see: Zirngibl et al. (1988). For related structures, see: Menini & Gusevskaya (2006); Baggaley & Watts (1982). For bond-length data, see: Allen et al. (1987).

Experimental top

Phenol (47.0 g, 0.5 mol), CuCl₂ (147.4 g, 1.1 mol) and hydrochloric acid (350 ml, 8.5 mol/L) were mixed in a three-necked flask equipped with a reflux condenser and a magnetic stirrer. The solution was stirred at 383 K for 10 h, and then cooled to room temperature. Subsequently the reaction mixture was extracted with toluene for three times, and then the extracts were dried and the solvents were completely stripped by evaporation. After isolated by column chromatography (silica), p-chlorophenol was obtained (yield; 44.8 g, 75%) (Menini & Gusevskaya, 2006). p-Chlorophenol (26.0 g, 0.2 mol) was dissolved with stirring in water (30 ml) containing sodium hydroxide (9.0 g, 0.23 mol) and added dropwise to excess refluxing ethylene dibromide (74.8 g, 0.4 mol). The reaction mixture was heated under reflux for 6 h, cooled and extracted into ether (3 x 150 ml). The combined organic extracts were washed with water, dried over Na₂S0₄, filtered and evaporated to dryness to yield an oil. Fractionation under reduced pressure yielded p-chlorophenoxyethyl bromide as a colorless oil, then cooled to give the title compound as colorless solid (yield; 27.6 g, 57%) (Baggaley & Watts, 1982). Crystals suitable for X-ray analysis were obtained by slow evaporation of an petroleum ether solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

1-(3-Bromopropoxy)-4-chlorobenzene top

Crystal data top

C₈H₈BrClO	F(000) = 464
M_r = 235.50	D_x = 1.740 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 9.0680 (18) Å	θ = 10–14°
b = 9.781 (2) Å	µ = 4.81 mm⁻¹
c = 10.238 (2) Å	T = 294 K
β = 98.01 (3)°	Block, colorless
V = 899.2 (3) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Enraf-Nonius CAD-4 diffractometer	769 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.327, T_max = 0.382	l = −12→12
1726 measured reflections	3 standard reflections every 120 min
1620 independent reflections	intensity decay: 1%

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.050P)² + 3.3P] where P = (F_o² + 2F_c²)/3
1620 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₈H₈BrClO	V = 899.2 (3) Å³
M_r = 235.50	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0680 (18) Å	µ = 4.81 mm⁻¹
b = 9.781 (2) Å	T = 294 K
c = 10.238 (2) Å	0.30 × 0.20 × 0.20 mm
β = 98.01 (3)°

Data collection top

Enraf-Nonius CAD-4 diffractometer	769 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.060
T_min = 0.327, T_max = 0.382	3 standard reflections every 120 min
1726 measured reflections	intensity decay: 1%
1620 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	0 restraints
wR(F²) = 0.166	H-atom parameters constrained
S = 1.00	Δρ_max = 0.48 e Å⁻³
1620 reflections	Δρ_min = −0.51 e Å⁻³
100 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	0.57689 (14)	−0.36443 (12)	0.40395 (11)	0.0876 (5)
Cl	−0.1214 (3)	−0.4586 (3)	−0.3126 (3)	0.0960 (10)
O	0.3720 (7)	−0.3636 (6)	0.1096 (6)	0.0663 (18)
C1	0.5206 (10)	−0.2276 (10)	0.2666 (9)	0.064 (2)
H1A	0.5247	−0.1379	0.3073	0.077*
H1B	0.5933	−0.2292	0.2056	0.077*
C2	0.3720 (10)	−0.2470 (10)	0.1918 (9)	0.064 (2)
H2A	0.2995	−0.2589	0.2522	0.077*
H2B	0.3443	−0.1667	0.1383	0.077*
C3	0.2602 (12)	−0.3856 (11)	0.0161 (11)	0.071 (3)
C4	0.1241 (11)	−0.3031 (10)	0.0054 (9)	0.066 (2)
H4A	0.1144	−0.2325	0.0644	0.079*
C5	0.0111 (12)	−0.3336 (11)	−0.0948 (10)	0.074 (3)
H5A	−0.0765	−0.2832	−0.1003	0.089*
C6	0.0200 (10)	−0.4318 (10)	−0.1849 (8)	0.061 (2)
C7	0.1567 (11)	−0.5088 (10)	−0.1676 (10)	0.070 (3)
H7A	0.1688	−0.5780	−0.2276	0.084*
C8	0.2624 (10)	−0.4863 (10)	−0.0733 (9)	0.062 (2)
H8A	0.3455	−0.5430	−0.0661	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.1226 (10)	0.0711 (7)	0.0759 (7)	0.0158 (7)	0.0374 (6)	−0.0003 (7)
Cl	0.088 (2)	0.101 (2)	0.099 (2)	−0.0010 (18)	0.0109 (17)	−0.0052 (19)
O	0.092 (5)	0.052 (4)	0.067 (4)	−0.006 (4)	0.052 (4)	−0.013 (4)
C1	0.069 (5)	0.058 (5)	0.070 (5)	−0.001 (5)	0.022 (4)	−0.005 (5)
C2	0.072 (5)	0.051 (5)	0.074 (5)	−0.001 (4)	0.023 (4)	−0.011 (5)
C3	0.068 (5)	0.074 (6)	0.077 (5)	0.002 (5)	0.032 (5)	−0.004 (5)
C4	0.085 (6)	0.050 (5)	0.069 (5)	0.003 (4)	0.031 (4)	0.001 (4)
C5	0.075 (5)	0.074 (6)	0.079 (5)	0.010 (5)	0.032 (4)	0.010 (5)
C6	0.066 (5)	0.062 (5)	0.055 (4)	−0.001 (4)	0.008 (4)	0.019 (4)
C7	0.078 (6)	0.059 (5)	0.075 (5)	0.001 (4)	0.021 (4)	0.000 (5)
C8	0.062 (5)	0.055 (5)	0.073 (5)	0.008 (4)	0.021 (4)	0.005 (4)

Geometric parameters (Å, º) top

Br—C1	1.957 (9)	C3—C4	1.466 (13)
Cl—C6	1.719 (10)	C4—C5	1.378 (13)
O—C3	1.311 (11)	C4—H4A	0.9300
O—C2	1.418 (10)	C5—C6	1.342 (13)
C1—C2	1.466 (12)	C5—H5A	0.9300
C1—H1A	0.9700	C6—C7	1.440 (13)
C1—H1B	0.9700	C7—C8	1.281 (12)
C2—H2A	0.9700	C7—H7A	0.9300
C2—H2B	0.9700	C8—H8A	0.9300
C3—C8	1.347 (13)

C3—O—C2	120.1 (8)	C5—C4—C3	117.9 (10)
C2—C1—Br	114.6 (6)	C5—C4—H4A	121.1
C2—C1—H1A	108.6	C3—C4—H4A	121.1
Br—C1—H1A	108.6	C6—C5—C4	123.8 (10)
C2—C1—H1B	108.6	C6—C5—H5A	118.1
Br—C1—H1B	108.6	C4—C5—H5A	118.1
H1A—C1—H1B	107.6	C5—C6—C7	115.1 (9)
O—C2—C1	109.8 (8)	C5—C6—Cl	121.4 (8)
O—C2—H2A	109.7	C7—C6—Cl	123.5 (8)
C1—C2—H2A	109.7	C8—C7—C6	122.9 (10)
O—C2—H2B	109.7	C8—C7—H7A	118.6
C1—C2—H2B	109.7	C6—C7—H7A	118.6
H2A—C2—H2B	108.2	C7—C8—C3	123.9 (10)
O—C3—C8	122.2 (9)	C7—C8—H8A	118.0
O—C3—C4	121.4 (10)	C3—C8—H8A	118.0
C8—C3—C4	116.3 (10)

C3—O—C2—C1	−167.0 (8)	C4—C5—C6—C7	2.1 (14)
Br—C1—C2—O	−70.5 (8)	C4—C5—C6—Cl	−176.5 (7)
C2—O—C3—C8	172.7 (8)	C5—C6—C7—C8	0.2 (14)
C2—O—C3—C4	−8.7 (13)	Cl—C6—C7—C8	178.8 (8)
O—C3—C4—C5	−179.4 (9)	C6—C7—C8—C3	−2.9 (15)
C8—C3—C4—C5	−0.7 (13)	O—C3—C8—C7	−178.4 (9)
C3—C4—C5—C6	−1.8 (14)	C4—C3—C8—C7	3.0 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cg1ⁱ	0.97	2.88	3.665 (3)	138

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₈BrClO
M_r	235.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	9.0680 (18), 9.781 (2), 10.238 (2)
β (°)	98.01 (3)
V (Å³)	899.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.81
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.327, 0.382
No. of measured, independent and observed [I > 2σ(I)] reflections	1726, 1620, 769
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.166, 1.00
No. of reflections	1620
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.51

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cg1ⁱ	0.97	2.883	3.665 (3)	138

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

This research was financially supported by the Department of Science and Technology of Jiangsu Province (grant No. BE200830457) and the `863' project (grant No. 2007 A A02Z211) of the Ministry of Science and Technology of the People's Republic of China.

References

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