1-(3-Bromopropoxy)-4-chlorobenzene

Abstract

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,

• a = 9.0680 (18) Å

• b = 9.781 (2) Å

• c = 10.238 (2) Å

• β = 98.01 (3)°

• V = 899.2 (3) ų

• 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[F ² > 2σ(F ²)] = 0.078

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) . Cg1 is the centroid of the C3–C8 ring.

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically, with C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

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

Crystal data

C8H8BrClO	F000 = 464
Mr = 235.50	Dx = 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 = 10–14º
b = 9.781 (2) Å	µ = 4.81 mm−1
c = 10.238 (2) Å	T = 294 (2) K
β = 98.01 (3)º	Block, colorless
V = 899.2 (3) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.060
Radiation source: fine-focus sealed tube	θmax = 25.3º
Monochromator: graphite	θmin = 2.3º
T = 294(2) K	h = 0→10
ω/2θ scans	k = 0→11
Absorption correction: ψ scan(North et al., 1968)	l = −12→12
Tmin = 0.327, Tmax = 0.382	3 standard reflections
1726 measured reflections	every 120 min
1620 independent reflections	intensity decay: 1%
769 reflections with I > 2σ(I)

Refinement

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)] = 0.078	H-atom parameters constrained
wR(F2) = 0.166	w = 1/[σ2(Fo2) + (0.050P)2 + 3.3P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1620 reflections	Δρmax = 0.48 e Å−3
100 parameters	Δρmin = −0.51 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) x, −y+1/2, z−1/2.