organic compounds
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
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 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 ); Marvel et al. (1953). Their utility is discussed by Trost & Fleming (1991).
has been known for a long time; see: Buck & Heilbron (1922Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell 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
10.1107/S1600536809009386/bt2898sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809009386/bt2898Isup2.hkl
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).
Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.99 Å) and were included in the
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.
Data collection: APEX2 (Bruker, 2008); cell
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).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. |
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 |
Bruker SMART APEX diffractometer | 2040 independent reflections |
Radiation source: fine-focus sealed tube | 1797 reflections with I > 2σ(I) |
Graphite monochromator | 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 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 |
C10H9BrO2 | γ = 94.468 (2)° |
Mr = 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)° |
Bruker SMART APEX diffractometer | 2040 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1797 reflections with I > 2σ(I) |
Tmin = 0.268, Tmax = 0.916 | Rint = 0.025 |
3659 measured reflections |
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 | Δρmax = 0.66 e Å−3 |
2040 reflections | Δρmin = −0.58 e Å−3 |
123 parameters |
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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.268, 0.916 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3659, 2040, 1797 |
Rint | 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 |
Δρmax, Δρmin (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).
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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