4-(5-Bromo-2-hydroxy­phen­yl)but-3-ene-2-one

Abstract

The molecule of the title compound, C₁₀H₉BrO₂, a doubly conjugated unsaturated ketone, is almost planar (r.m.s. deviation of the non-H atoms = 0.039 Å). In the crystal structure, two mol­ecules are linked across a centre of inversion to form a hydrogen-bonded dimer by way of two O—H⋯O links.

Related literature

The reactivity of doubly conjugated unsaturated ketones has been known for a long time; see: Buck & Heilbron (1922 ▶); Marvel et al. (1953 ▶). Their utility is discussed by Trost & Fleming (1991 ▶).

Experimental

Crystal data

• C₁₀H₉BrO₂

• M _r = 241.08

• Triclinic,

• a = 5.8619 (2) Å

• b = 7.7495 (2) Å

• c = 10.9601 (3) Å

• α = 106.432 (2)°

• β = 104.548 (2)°

• γ = 94.468 (2)°

• V = 456.25 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 4.47 mm⁻¹

• T = 123 K

• 0.40 × 0.10 × 0.02 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.268, T _max = 0.916

• 3659 measured reflections

• 2040 independent reflections

• 1797 reflections with I > 2σ(I)

• R _int = 0.025

Refinement

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.074

• S = 1.04

• 2040 reflections

• 123 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.66 e Å⁻³

• Δρ_min = −0.58 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

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
O1—H1⋯O2i	0.83 (1)	1.87 (1)	2.689 (3)	168 (4)

Symmetry code: (i) .

supplementary crystallographic information

Experimental

To a stirred solution of 5-bromo-2-hydroxy-benzaldehyde (1.01 g, 5 mmol) in acetone (50 ml) a solution of sodium hydroxide (1.25 g, 6 mmol) in water (20 ml) was added. The reaction was stirred for another 6 h before being neutralized with strong hydrochloric acid to a pH of 6. The organic phase was washed by aqueous solution of sodium bisulfate (40%). After removing the solvent, the light green powder recrystallized from dichloromethane to give colorless plates (yield 85%, m.p. 421 K).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The hydroxy H-atom was located in a difference Fourier map, and was refined with a distance restraint of O–H 0.84±0.01 Å.

Figures

Fig. 1.

Anisotropic displacement ellisoid plot (Barbour, 2001) of C10H9BrNO2; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.

Crystal data

C10H9BrO2	Z = 2
Mr = 241.08	F(000) = 240
Triclinic, P1	Dx = 1.755 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8619 (2) Å	Cell parameters from 1830 reflections
b = 7.7495 (2) Å	θ = 2.8–28.1°
c = 10.9601 (3) Å	µ = 4.47 mm−1
α = 106.432 (2)°	T = 123 K
β = 104.548 (2)°	Plate, colorless
γ = 94.468 (2)°	0.40 × 0.10 × 0.02 mm
V = 456.25 (2) Å3

Data collection

Bruker SMART APEX diffractometer	2040 independent reflections
Radiation source: fine-focus sealed tube	1797 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.268, Tmax = 0.916	k = −10→9
3659 measured reflections	l = −14→14

Refinement

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0287P)2 + 0.4716P] where P = (Fo2 + 2Fc2)/3
2040 reflections	(Δ/σ)max = 0.001
123 parameters	Δρmax = 0.66 e Å−3
1 restraint	Δρmin = −0.58 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.69822 (5)	0.19383 (4)	−0.18504 (3)	0.02165 (11)
O1	0.3724 (4)	0.3898 (3)	0.3090 (2)	0.0231 (5)
H1	0.256 (4)	0.319 (4)	0.307 (4)	0.033 (11)*
O2	0.9820 (4)	0.8201 (3)	0.6596 (2)	0.0226 (5)
C1	0.4405 (5)	0.3456 (4)	0.1967 (3)	0.0173 (6)
C2	0.2974 (5)	0.2178 (4)	0.0796 (3)	0.0188 (6)
H2	0.1468	0.1611	0.0782	0.023*
C3	0.3699 (5)	0.1715 (4)	−0.0348 (3)	0.0192 (6)
H3	0.2722	0.0828	−0.1138	0.023*
C4	0.5894 (5)	0.2583 (4)	−0.0309 (3)	0.0173 (6)
C5	0.7326 (5)	0.3867 (4)	0.0822 (3)	0.0168 (6)
H5	0.8812	0.4441	0.0815	0.020*
C6	0.6617 (5)	0.4341 (4)	0.1992 (3)	0.0166 (6)
C7	0.8291 (5)	0.5694 (4)	0.3152 (3)	0.0178 (6)
H7	0.9703	0.6173	0.3004	0.021*
C8	0.8136 (5)	0.6359 (4)	0.4390 (3)	0.0180 (6)
H8	0.6731	0.5958	0.4582	0.022*
C10	1.2237 (6)	0.8416 (4)	0.5192 (3)	0.0248 (7)
H10A	1.3292	0.9287	0.6014	0.037*
H10B	1.1786	0.9032	0.4521	0.037*
H10C	1.3071	0.7412	0.4868	0.037*
C9	1.0023 (5)	0.7671 (4)	0.5460 (3)	0.0177 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.02299 (17)	0.02469 (17)	0.01502 (15)	−0.00029 (11)	0.00787 (11)	0.00169 (11)
O1	0.0206 (11)	0.0277 (12)	0.0199 (11)	−0.0035 (9)	0.0101 (9)	0.0037 (9)
O2	0.0263 (12)	0.0215 (11)	0.0178 (10)	−0.0001 (9)	0.0082 (9)	0.0025 (9)
C1	0.0201 (15)	0.0182 (14)	0.0161 (14)	0.0048 (11)	0.0067 (12)	0.0073 (11)
C2	0.0198 (15)	0.0189 (14)	0.0195 (14)	0.0013 (12)	0.0071 (12)	0.0080 (12)
C3	0.0196 (15)	0.0188 (14)	0.0160 (14)	0.0021 (12)	0.0023 (12)	0.0035 (11)
C4	0.0213 (15)	0.0173 (14)	0.0165 (13)	0.0068 (12)	0.0099 (12)	0.0054 (11)
C5	0.0147 (14)	0.0193 (14)	0.0189 (14)	0.0032 (11)	0.0066 (11)	0.0079 (11)
C6	0.0179 (14)	0.0157 (14)	0.0158 (13)	0.0031 (11)	0.0047 (11)	0.0047 (11)
C7	0.0157 (14)	0.0193 (14)	0.0189 (14)	0.0026 (11)	0.0043 (12)	0.0074 (12)
C8	0.0153 (14)	0.0181 (14)	0.0205 (14)	0.0011 (11)	0.0057 (12)	0.0056 (12)
C10	0.0215 (16)	0.0251 (16)	0.0223 (15)	−0.0054 (13)	0.0070 (13)	0.0005 (13)
C9	0.0205 (15)	0.0150 (14)	0.0179 (14)	0.0025 (11)	0.0059 (12)	0.0056 (11)

Geometric parameters (Å, °)

Br1—C4	1.903 (3)	C5—C6	1.406 (4)
O1—C1	1.350 (3)	C5—H5	0.9500
O1—H1	0.834 (10)	C6—C7	1.461 (4)
O2—C9	1.235 (3)	C7—C8	1.338 (4)
C1—C2	1.394 (4)	C7—H7	0.9500
C1—C6	1.409 (4)	C8—C9	1.460 (4)
C2—C3	1.385 (4)	C8—H8	0.9500
C2—H2	0.9500	C10—C9	1.508 (4)
C3—C4	1.390 (4)	C10—H10A	0.9800
C3—H3	0.9500	C10—H10B	0.9800
C4—C5	1.371 (4)	C10—H10C	0.9800
C1—O1—H1	114 (3)	C5—C6—C7	116.5 (3)
O1—C1—C2	121.9 (3)	C1—C6—C7	125.4 (3)
O1—C1—C6	118.3 (3)	C8—C7—C6	129.8 (3)
C2—C1—C6	119.8 (3)	C8—C7—H7	115.1
C3—C2—C1	121.5 (3)	C6—C7—H7	115.1
C3—C2—H2	119.2	C7—C8—C9	123.1 (3)
C1—C2—H2	119.2	C7—C8—H8	118.5
C2—C3—C4	118.2 (3)	C9—C8—H8	118.5
C2—C3—H3	120.9	C9—C10—H10A	109.5
C4—C3—H3	120.9	C9—C10—H10B	109.5
C5—C4—C3	121.6 (3)	H10A—C10—H10B	109.5
C5—C4—Br1	119.0 (2)	C9—C10—H10C	109.5
C3—C4—Br1	119.3 (2)	H10A—C10—H10C	109.5
C4—C5—C6	120.7 (3)	H10B—C10—H10C	109.5
C4—C5—H5	119.6	O2—C9—C8	120.5 (3)
C6—C5—H5	119.6	O2—C9—C10	119.0 (3)
C5—C6—C1	118.1 (3)	C8—C9—C10	120.5 (3)
O1—C1—C2—C3	−179.2 (2)	O1—C1—C6—C5	179.6 (2)
C6—C1—C2—C3	1.6 (4)	C2—C1—C6—C5	−1.2 (4)
C1—C2—C3—C4	−1.0 (4)	O1—C1—C6—C7	1.2 (4)
C2—C3—C4—C5	0.0 (4)	C2—C1—C6—C7	−179.5 (3)
C2—C3—C4—Br1	178.5 (2)	C5—C6—C7—C8	−177.8 (3)
C3—C4—C5—C6	0.4 (4)	C1—C6—C7—C8	0.6 (5)
Br1—C4—C5—C6	−178.10 (19)	C6—C7—C8—C9	177.6 (3)
C4—C5—C6—C1	0.2 (4)	C7—C8—C9—O2	−177.8 (3)
C4—C5—C6—C7	178.7 (2)	C7—C8—C9—C10	2.9 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.83 (1)	1.87 (1)	2.689 (3)	168 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.