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Acta Cryst. (2009). E65, o795    [ doi:10.1107/S1600536809009386 ]

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

A. Zonouzi, Z. Izakiana, H. Rahmani and S. W. Ng

Abstract top

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 top

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 top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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).

Figures top
[Figure 1] 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.
4-(5-Bromo-2-hydroxyphenyl)but-3-ene-2-one top
Crystal data top
C10H9BrO2Z = 2
Mr = 241.08F(000) = 240
Triclinic, P1Dx = 1.755 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.8619 (2) ÅCell parameters from 1830 reflections
b = 7.7495 (2) Åθ = 2.8–28.1°
c = 10.9601 (3) ŵ = 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 top
Bruker SMART APEX
diffractometer		2040 independent reflections
Radiation source: fine-focus sealed tube1797 reflections with I > 2σ(I)
graphiteRint = 0.025
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.268, Tmax = 0.916k = −10→9
3659 measured reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H 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 parametersΔρmax = 0.66 e Å−3
1 restraintΔρmin = −0.58 e Å−3
Crystal data top
C10H9BrO2γ = 94.468 (2)°
Mr = 241.08V = 456.25 (2) Å3
Triclinic, P1Z = 2
a = 5.8619 (2) ÅMo Kα radiation
b = 7.7495 (2) ŵ = 4.47 mm−1
c = 10.9601 (3) ÅT = 123 K
α = 106.432 (2)°0.40 × 0.10 × 0.02 mm
β = 104.548 (2)°
Data collection top
Bruker SMART APEX
diffractometer		2040 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1797 reflections with I > 2σ(I)
Tmin = 0.268, Tmax = 0.916Rint = 0.025
3659 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074Δρmax = 0.66 e Å−3
S = 1.04Δρmin = −0.58 e Å−3
2040 reflectionsAbsolute structure: ?
123 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.69822 (5)0.19383 (4)−0.18504 (3)0.02165 (11)
O10.3724 (4)0.3898 (3)0.3090 (2)0.0231 (5)
H10.256 (4)0.319 (4)0.307 (4)0.033 (11)*
O20.9820 (4)0.8201 (3)0.6596 (2)0.0226 (5)
C10.4405 (5)0.3456 (4)0.1967 (3)0.0173 (6)
C20.2974 (5)0.2178 (4)0.0796 (3)0.0188 (6)
H20.14680.16110.07820.023*
C30.3699 (5)0.1715 (4)−0.0348 (3)0.0192 (6)
H30.27220.0828−0.11380.023*
C40.5894 (5)0.2583 (4)−0.0309 (3)0.0173 (6)
C50.7326 (5)0.3867 (4)0.0822 (3)0.0168 (6)
H50.88120.44410.08150.020*
C60.6617 (5)0.4341 (4)0.1992 (3)0.0166 (6)
C70.8291 (5)0.5694 (4)0.3152 (3)0.0178 (6)
H70.97030.61730.30040.021*
C80.8136 (5)0.6359 (4)0.4390 (3)0.0180 (6)
H80.67310.59580.45820.022*
C101.2237 (6)0.8416 (4)0.5192 (3)0.0248 (7)
H10A1.32920.92870.60140.037*
H10B1.17860.90320.45210.037*
H10C1.30710.74120.48680.037*
C91.0023 (5)0.7671 (4)0.5460 (3)0.0177 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02299 (17)0.02469 (17)0.01502 (15)−0.00029 (11)0.00787 (11)0.00169 (11)
O10.0206 (11)0.0277 (12)0.0199 (11)−0.0035 (9)0.0101 (9)0.0037 (9)
O20.0263 (12)0.0215 (11)0.0178 (10)−0.0001 (9)0.0082 (9)0.0025 (9)
C10.0201 (15)0.0182 (14)0.0161 (14)0.0048 (11)0.0067 (12)0.0073 (11)
C20.0198 (15)0.0189 (14)0.0195 (14)0.0013 (12)0.0071 (12)0.0080 (12)
C30.0196 (15)0.0188 (14)0.0160 (14)0.0021 (12)0.0023 (12)0.0035 (11)
C40.0213 (15)0.0173 (14)0.0165 (13)0.0068 (12)0.0099 (12)0.0054 (11)
C50.0147 (14)0.0193 (14)0.0189 (14)0.0032 (11)0.0066 (11)0.0079 (11)
C60.0179 (14)0.0157 (14)0.0158 (13)0.0031 (11)0.0047 (11)0.0047 (11)
C70.0157 (14)0.0193 (14)0.0189 (14)0.0026 (11)0.0043 (12)0.0074 (12)
C80.0153 (14)0.0181 (14)0.0205 (14)0.0011 (11)0.0057 (12)0.0056 (12)
C100.0215 (16)0.0251 (16)0.0223 (15)−0.0054 (13)0.0070 (13)0.0005 (13)
C90.0205 (15)0.0150 (14)0.0179 (14)0.0025 (11)0.0059 (12)0.0056 (11)
Geometric parameters (Å, °) top
Br1—C41.903 (3)C5—C61.406 (4)
O1—C11.350 (3)C5—H50.9500
O1—H10.834 (10)C6—C71.461 (4)
O2—C91.235 (3)C7—C81.338 (4)
C1—C21.394 (4)C7—H70.9500
C1—C61.409 (4)C8—C91.460 (4)
C2—C31.385 (4)C8—H80.9500
C2—H20.9500C10—C91.508 (4)
C3—C41.390 (4)C10—H10A0.9800
C3—H30.9500C10—H10B0.9800
C4—C51.371 (4)C10—H10C0.9800
C1—O1—H1114 (3)C5—C6—C7116.5 (3)
O1—C1—C2121.9 (3)C1—C6—C7125.4 (3)
O1—C1—C6118.3 (3)C8—C7—C6129.8 (3)
C2—C1—C6119.8 (3)C8—C7—H7115.1
C3—C2—C1121.5 (3)C6—C7—H7115.1
C3—C2—H2119.2C7—C8—C9123.1 (3)
C1—C2—H2119.2C7—C8—H8118.5
C2—C3—C4118.2 (3)C9—C8—H8118.5
C2—C3—H3120.9C9—C10—H10A109.5
C4—C3—H3120.9C9—C10—H10B109.5
C5—C4—C3121.6 (3)H10A—C10—H10B109.5
C5—C4—Br1119.0 (2)C9—C10—H10C109.5
C3—C4—Br1119.3 (2)H10A—C10—H10C109.5
C4—C5—C6120.7 (3)H10B—C10—H10C109.5
C4—C5—H5119.6O2—C9—C8120.5 (3)
C6—C5—H5119.6O2—C9—C10119.0 (3)
C5—C6—C1118.1 (3)C8—C9—C10120.5 (3)
O1—C1—C2—C3−179.2 (2)O1—C1—C6—C5179.6 (2)
C6—C1—C2—C31.6 (4)C2—C1—C6—C5−1.2 (4)
C1—C2—C3—C4−1.0 (4)O1—C1—C6—C71.2 (4)
C2—C3—C4—C50.0 (4)C2—C1—C6—C7−179.5 (3)
C2—C3—C4—Br1178.5 (2)C5—C6—C7—C8−177.8 (3)
C3—C4—C5—C60.4 (4)C1—C6—C7—C80.6 (5)
Br1—C4—C5—C6−178.10 (19)C6—C7—C8—C9177.6 (3)
C4—C5—C6—C10.2 (4)C7—C8—C9—O2−177.8 (3)
C4—C5—C6—C7178.7 (2)C7—C8—C9—C102.9 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.83 (1)1.87 (1)2.689 (3)168 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.83 (1)1.87 (1)2.689 (3)168 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors thank the Research Council of Tehran University and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Buck, J. S. & Heilbron, I. M. (1922). J. Chem. Soc. 121, 1095-1101.

Marvel, C. S., Quinn, J. M. & Showell, J. S. (1953). J. Org. Chem. 18, 1731–1738.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Trost, B. M. & Fleming, I. (1991). Comprehensive Organic Synthesis. London: Pergamon.

Westrip, S. P. (2009). publCIF. In preparation.