organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Buck, J. S. & Heilbron, I. M. (1922). J. Chem. Soc. 121, 1095-1101.]); Marvel et al. (1953[Marvel, C. S., Quinn, J. M. & Showell, J. S. (1953). J. Org. Chem. 18, 1731-1738.]). Their utility is discussed by Trost & Fleming (1991[Trost, B. M. & Fleming, I. (1991). Comprehensive Organic Synthesis. London: Pergamon.]).

[Scheme 1]

Experimental

Crystal data
  • C10H9BrO2

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.268, Tmax = 0.916

  • 3659 measured reflections

  • 2040 independent reflections

  • 1797 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.66 e Å−3

  • Δρmin = −0.58 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


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 m3
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 mm1
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)
Graphite monochromatorRint = 0.025
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 77
Tmin = 0.268, Tmax = 0.916k = 109
3659 measured reflectionsl = 1414
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 Å3
1 restraintΔρmin = 0.58 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.66 e Å3
2040 reflectionsΔρmin = 0.58 e Å3
123 parameters
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)
H30.27220.08280.11380.023*
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, º) 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—C3179.2 (2)O1—C1—C6—C5179.6 (2)
C6—C1—C2—C31.6 (4)C2—C1—C6—C51.2 (4)
C1—C2—C3—C41.0 (4)O1—C1—C6—C71.2 (4)
C2—C3—C4—C50.0 (4)C2—C1—C6—C7179.5 (3)
C2—C3—C4—Br1178.5 (2)C5—C6—C7—C8177.8 (3)
C3—C4—C5—C60.4 (4)C1—C6—C7—C80.6 (5)
Br1—C4—C5—C6178.10 (19)C6—C7—C8—C9177.6 (3)
C4—C5—C6—C10.2 (4)C7—C8—C9—O2177.8 (3)
C4—C5—C6—C7178.7 (2)C7—C8—C9—C102.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.83 (1)1.87 (1)2.689 (3)168 (4)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC10H9BrO2
Mr241.08
Crystal system, space groupTriclinic, 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)
V3)456.25 (2)
Z2
Radiation typeMo Kα
µ (mm1)4.47
Crystal size (mm)0.40 × 0.10 × 0.02
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.268, 0.916
No. of measured, independent and
observed [I > 2σ(I)] reflections
3659, 2040, 1797
Rint0.025
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.074, 1.04
No. of reflections2040
No. of parameters123
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1···O2i0.83 (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

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBuck, J. S. & Heilbron, I. M. (1922). J. Chem. Soc. 121, 1095–1101.  CrossRef CAS Google Scholar
First citationMarvel, C. S., Quinn, J. M. & Showell, J. S. (1953). J. Org. Chem. 18, 1731–1738.  Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTrost, B. M. & Fleming, I. (1991). Comprehensive Organic Synthesis. London: Pergamon.  Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar

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ISSN: 2056-9890
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