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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o2004.
Published online 2009 July 25. doi:  10.1107/S1600536809029067
PMCID: PMC2977251

1-(5-Bromo-2-hydr­oxy-4-methoxy­phen­yl)ethanone

Abstract

In the title compound, C9H9BrO3, the dihedral angle between the ethanone group and the aromatic ring is 3.6 (2)°. The mol­ecular conformation is consolidated by an intra­molecular O—H(...)O hydrogen bond. The crystal structure is stabilized by π–π inter­actions between the benzene rings [centroid–centroid distance = 3.588 (2) Å].

Related literature

1-(5-Bromo-2-hydr­oxy-4-methoxy­phen­yl)ethanone is one of the main components of the traditional Chinese medicine Moutan Cortex, which is also a valuable spice and is widely used in domestic chemistry, see: Chung (1999 [triangle]); Liu et al. (2000 [triangle]). For our work on the preparation of derivatives, see: Qi et al. (2003 [triangle]).

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Object name is e-65-o2004-scheme1.jpg

Experimental

Crystal data

  • C9H9BrO3
  • M r = 245.07
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2004-efi1.jpg
  • a = 9.916 (3) Å
  • b = 13.836 (5) Å
  • c = 6.940 (2) Å
  • β = 90.031 (3)°
  • V = 952.0 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.29 mm−1
  • T = 296 K
  • 0.24 × 0.13 × 0.09 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001 [triangle]) T min = 0.426, T max = 0.699
  • 5163 measured reflections
  • 1860 independent reflections
  • 977 reflections with I > 2σ(I)
  • R int = 0.080

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.068
  • S = 1.01
  • 1860 reflections
  • 118 parameters
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.52 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029067/at2849sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029067/at2849Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

1-(5-Bromo-2-hydroxy-4-methoxyphenyl)ethanone is one of the main components of traditional Chinese medicine Moutan Cortex, which is also a valuable inartificial spicery and can be widely used in domestic chemistry (Chung, 1999; Liu, et al. 2000). But the nature of water insolubility and volatility makes it difficult to exert its efficiency sufficiently. Preparing derivatives has been an active research area (Qi, et al. 2003) for a long time. Herein we report the crystal structure of the title compound (I).

Compound (I) consists of an asymmetric organic molecule (Fig.1). The C1—C6 benzene ring in (I) is an aromatic ring, on which four different organic groups decorated. In the structure, C8—O3 [1.224 (4) Å] is typical for a C═O double bond, whereas, the C4—O1, C6—O2 and C7—O2 bond distances are of 1.347 (4), 1.351 (4) and 1.420 (4) Å, respectively, indicating three obviously C—O single bonds.

In addition, the intramolecular hydrogen bond exhibit in the compound, O1—H1A acting as hydrogen bond donor, and O3 atom as hydrogen bond acceptor, constructing a S(6) ring (Fig.1, Table 1). The crystal structure is stabilized by π-π interactions between the benzene rings [centroid-to-centroid distance = 3.588 (2) Å].

Experimental

2-Hydroxyl-4-methoxyacetophenone was isolated from the Chinese medicine Moutan Cortex. N-Bromosuccinimide (0.534 g, 3 mmol) was added slowly by cannulation to a stirred suspension of 2-hydroxyl-4-methoxyacetophenone (0.499 g, 3 mmol) in chloroform (50 ml) at room temperature. After stirring for 1 h the solution was quenched with saturated aqueous sodium bicarbonate solution (20 ml) the layers were separated and the aqueous layer was extracted with chloroform, the combined organic extracts were washed with water (20 ml), dried (MgSO4) and evaporated under reduced pressure to give the crude product. Then purification by short column chromatography (chloroform) and recrystallization from chloroform gave the compound (I) as needle-like colourless crystal (0.645 g, 88%).

Refinement

H atoms were treated as riding, with C—H distances of 0.93 Å–0.96 Å and O—H distances of 0.82 Å, and were refined as riding with Uiso(H) = 1.2Ueq(C in aromatic ring) and Uiso(H) = 1.5Ueq(O or Cmethyl).

Figures

Fig. 1.
The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. An intramolecular O—H···O hydrogen bond is indicated by the dashed line.

Crystal data

C9H9BrO3F(000) = 488
Mr = 245.07Dx = 1.710 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1164 reflections
a = 9.916 (3) Åθ = 2.5–21.4°
b = 13.836 (5) ŵ = 4.29 mm1
c = 6.940 (2) ÅT = 296 K
β = 90.031 (3)°Needle-like, colourless
V = 952.0 (5) Å30.24 × 0.13 × 0.09 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1860 independent reflections
Radiation source: fine-focus sealed tube977 reflections with I > 2σ(I)
graphiteRint = 0.080
[var phi] and ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)h = −12→9
Tmin = 0.426, Tmax = 0.699k = −17→16
5163 measured reflectionsl = −8→8

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.001P)2] where P = (Fo2 + 2Fc2)/3
1860 reflections(Δ/σ)max = 0.001
118 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.52 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
Br10.67087 (5)0.52356 (3)0.17229 (7)0.0635 (2)
O11.0051 (3)0.88085 (17)0.2857 (4)0.0522 (8)
H1A1.08390.86820.31090.078*
O20.5841 (3)0.7279 (2)0.1634 (4)0.0514 (8)
O31.2075 (3)0.7721 (2)0.3509 (4)0.0625 (9)
C10.7770 (4)0.6352 (3)0.2110 (5)0.0377 (11)
C20.9133 (4)0.6264 (3)0.2495 (5)0.0398 (11)
H2A0.95150.56510.25720.048*
C30.9948 (4)0.7076 (3)0.2771 (5)0.0336 (10)
C40.9349 (4)0.7981 (3)0.2651 (5)0.0379 (11)
C50.7969 (4)0.8080 (3)0.2272 (5)0.0393 (11)
H5A0.75840.86920.22000.047*
C60.7179 (4)0.7270 (3)0.2006 (5)0.0382 (11)
C70.5177 (4)0.8188 (3)0.1589 (7)0.0638 (14)
H7A0.42380.80930.13080.096*
H7B0.55750.85860.06100.096*
H7C0.52690.84990.28190.096*
C81.1410 (5)0.6994 (3)0.3182 (6)0.0445 (12)
C91.2063 (4)0.6027 (3)0.3192 (7)0.0649 (14)
H9A1.30050.60970.34820.097*
H9B1.19620.57320.19480.097*
H9C1.16450.56270.41510.097*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0606 (3)0.0477 (3)0.0823 (4)−0.0137 (3)−0.0044 (3)−0.0034 (3)
O10.051 (2)0.0372 (19)0.069 (2)−0.0123 (15)0.0022 (16)0.0005 (16)
O20.038 (2)0.051 (2)0.065 (2)0.0066 (16)−0.0004 (16)0.0018 (16)
O30.043 (2)0.068 (2)0.077 (2)−0.0145 (17)−0.0017 (17)−0.0097 (19)
C10.045 (3)0.033 (3)0.036 (3)−0.003 (2)0.005 (2)0.002 (2)
C20.043 (3)0.038 (3)0.038 (3)0.008 (2)0.000 (2)0.001 (2)
C30.035 (3)0.035 (3)0.030 (3)0.001 (2)−0.001 (2)−0.002 (2)
C40.044 (3)0.037 (3)0.033 (3)−0.009 (2)0.010 (2)0.001 (2)
C50.051 (3)0.030 (3)0.037 (3)0.004 (2)0.004 (2)0.003 (2)
C60.035 (3)0.048 (3)0.031 (3)0.003 (2)0.007 (2)−0.002 (2)
C70.037 (3)0.081 (4)0.074 (4)0.015 (3)0.001 (3)0.008 (3)
C80.049 (3)0.048 (3)0.036 (3)0.000 (3)0.007 (2)−0.004 (2)
C90.041 (3)0.076 (4)0.078 (4)0.009 (3)−0.016 (3)−0.006 (3)

Geometric parameters (Å, °)

Br1—C11.889 (4)C3—C81.482 (5)
O1—C41.347 (4)C4—C51.400 (5)
O1—H1A0.8200C5—C61.380 (5)
O2—C61.351 (4)C5—H5A0.9300
O2—C71.420 (4)C7—H7A0.9600
O3—C81.224 (4)C7—H7B0.9600
C1—C21.382 (5)C7—H7C0.9600
C1—C61.400 (5)C8—C91.487 (5)
C2—C31.397 (5)C9—H9A0.9600
C2—H2A0.9300C9—H9B0.9600
C3—C41.389 (5)C9—H9C0.9600
C4—O1—H1A109.5O2—C6—C1115.5 (4)
C6—O2—C7117.9 (3)C5—C6—C1119.4 (4)
C2—C1—C6120.0 (4)O2—C7—H7A109.5
C2—C1—Br1120.0 (3)O2—C7—H7B109.5
C6—C1—Br1120.0 (3)H7A—C7—H7B109.5
C1—C2—C3121.4 (4)O2—C7—H7C109.5
C1—C2—H2A119.3H7A—C7—H7C109.5
C3—C2—H2A119.3H7B—C7—H7C109.5
C4—C3—C2118.0 (4)O3—C8—C3120.0 (4)
C4—C3—C8119.9 (4)O3—C8—C9120.3 (4)
C2—C3—C8122.1 (4)C3—C8—C9119.7 (4)
O1—C4—C3122.6 (4)C8—C9—H9A109.5
O1—C4—C5116.2 (4)C8—C9—H9B109.5
C3—C4—C5121.1 (4)H9A—C9—H9B109.5
C6—C5—C4120.0 (4)C8—C9—H9C109.5
C6—C5—H5A120.0H9A—C9—H9C109.5
C4—C5—H5A120.0H9B—C9—H9C109.5
O2—C6—C5125.1 (4)
C6—C1—C2—C3−0.5 (6)C7—O2—C6—C1177.5 (4)
Br1—C1—C2—C3179.4 (3)C4—C5—C6—O2180.0 (3)
C1—C2—C3—C40.1 (6)C4—C5—C6—C1−0.3 (6)
C1—C2—C3—C8−179.9 (3)C2—C1—C6—O2−179.6 (3)
C2—C3—C4—O1−178.7 (4)Br1—C1—C6—O20.4 (5)
C8—C3—C4—O11.4 (5)C2—C1—C6—C50.6 (6)
C2—C3—C4—C50.2 (5)Br1—C1—C6—C5−179.3 (3)
C8—C3—C4—C5−179.8 (3)C4—C3—C8—O33.6 (6)
O1—C4—C5—C6178.8 (3)C2—C3—C8—O3−176.4 (4)
C3—C4—C5—C6−0.1 (6)C4—C3—C8—C9−176.3 (4)
C7—O2—C6—C5−2.7 (5)C2—C3—C8—C93.7 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···O30.821.832.549 (4)146

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2849).

References

  • Bruker (2001). SAINT-Plus and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chung, J. G. (1999). Food Chem. Toxicol.37, 327–334. [PubMed]
  • Liu, C. Y., Wu, Y. Z., Zhou, D. X. & Wang, C. P. (2000). J. Biol.17, 23–24.
  • Qi, J. S., Chao, Y. & Wang, Y. L. (2003). Chin. J. Appl. Chem.20, 702–703.
  • Sheldrick, G. M. (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography