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

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

doi:10.1107/S1600536809009386

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o795

doi:10.1107/S1600536809009386

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

Afsaneh Zonouzi,^a Zakieh Izakiana,^a Hossein Rahmani ^b and Seik Weng Ng ^c ^*

^aDepartment of Chemistry, College of Science, University of Tehran, PO Box 13145-143, Tehran, Iran, ^bInstitute of Chemical Industries, Iranian Research Organization for Science and Technology, PO Box 15815-358, Tehran, Iran, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 March 2009; accepted 13 March 2009; online 19 March 2009)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.031
wR(F²) = 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

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) -x+1, -y+1, -z+1.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009386/bt2898sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009386/bt2898Isup2.hkl

checkCIF report

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).

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

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

C₁₀H₉BrO₂	Z = 2
M_r = 241.08	F(000) = 240
Triclinic, P1	D_x = 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 top

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

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)] = 0.031	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(F_o²) + (0.0287P)² + 0.4716P] where P = (F_o² + 2F_c²)/3
2040 reflections	(Δ/σ)_max = 0.001
123 parameters	Δρ_max = 0.66 e Å⁻³
1 restraint	Δρ_min = −0.58 e Å⁻³

Crystal data top

C₁₀H₉BrO₂	γ = 94.468 (2)°
M_r = 241.08	V = 456.25 (2) Å³
Triclinic, P1	Z = 2
a = 5.8619 (2) Å	Mo Kα radiation
b = 7.7495 (2) Å	µ = 4.47 mm⁻¹
c = 10.9601 (3) Å	T = 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)
T_min = 0.268, T_max = 0.916	R_int = 0.025
3659 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	1 restraint
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.66 e Å⁻³
2040 reflections	Δρ_min = −0.58 e Å⁻³
123 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₉BrO₂
M_r	241.08
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	5.8619 (2), 7.7495 (2), 10.9601 (3)
α, β, γ (°)	106.432 (2), 104.548 (2), 94.468 (2)
V (Å³)	456.25 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.47
Crystal size (mm)	0.40 × 0.10 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.268, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	3659, 2040, 1797
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.074, 1.04
No. of reflections	2040
No. of parameters	123
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.58

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+1.

Acknowledgements

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

References

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