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

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ISSN: 2056-9890

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

aMedical College of Henan University, Henan University, Kaifeng 475004, People's Republic of China, and bHenan Quality Polytechnic, Pingdingshan, 467000, People's Republic of China
*Correspondence e-mail: ysum@yahoo.cn

(Received 21 July 2009; accepted 22 July 2009; online 25 July 2009)

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 ππ 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[Chung, J. G. (1999). Food Chem. Toxicol. 37, 327-334.]); Liu et al. (2000[Liu, C. Y., Wu, Y. Z., Zhou, D. X. & Wang, C. P. (2000). J. Biol. 17, 23-24.]). For our work on the preparation of derivatives, see: Qi et al. (2003[Qi, J. S., Chao, Y. & Wang, Y. L. (2003). Chin. J. Appl. Chem. 20, 702-703.]).

[Scheme 1]

Experimental

Crystal data
  • C9H9BrO3

  • Mr = 245.07

  • Monoclinic, P 21 /c

  • 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[Sheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.426, Tmax = 0.699

  • 5163 measured reflections

  • 1860 independent reflections

  • 977 reflections with I > 2σ(I)

  • Rint = 0.080

Refinement
  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1A⋯O3 0.82 1.83 2.549 (4) 146

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2001[Bruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; 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: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: PLATON.

Supporting information


Comment top

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 CO 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].

Related literature top

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 can be widely used in domestic chemistry, see: Chung (1999); Liu et al. (2000). For our work on the preparation of derivatives, see: Qi et al. (2003).

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] 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.
1-(5-Bromo-2-hydroxy-4-methoxyphenyl)ethanone top
Crystal data top
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 top
Bruker SMART CCD area-detector
diffractometer
1860 independent reflections
Radiation source: fine-focus sealed tube977 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.080
ϕ and ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 129
Tmin = 0.426, Tmax = 0.699k = 1716
5163 measured reflectionsl = 88
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 1.01 w = 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
Crystal data top
C9H9BrO3V = 952.0 (5) Å3
Mr = 245.07Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.916 (3) ŵ = 4.29 mm1
b = 13.836 (5) ÅT = 296 K
c = 6.940 (2) Å0.24 × 0.13 × 0.09 mm
β = 90.031 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1860 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
977 reflections with I > 2σ(I)
Tmin = 0.426, Tmax = 0.699Rint = 0.080
5163 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.068H-atom parameters constrained
S = 1.01Δρmax = 0.46 e Å3
1860 reflectionsΔρmin = 0.52 e Å3
118 parameters
Special details top

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) top
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) top
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, º) top
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—C30.5 (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—C10.3 (6)
C1—C2—C3—C8179.9 (3)C2—C1—C6—O2179.6 (3)
C2—C3—C4—O1178.7 (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—C5179.3 (3)
C8—C3—C4—C5179.8 (3)C4—C3—C8—O33.6 (6)
O1—C4—C5—C6178.8 (3)C2—C3—C8—O3176.4 (4)
C3—C4—C5—C60.1 (6)C4—C3—C8—C9176.3 (4)
C7—O2—C6—C52.7 (5)C2—C3—C8—C93.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O30.821.832.549 (4)146

Experimental details

Crystal data
Chemical formulaC9H9BrO3
Mr245.07
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)9.916 (3), 13.836 (5), 6.940 (2)
β (°) 90.031 (3)
V3)952.0 (5)
Z4
Radiation typeMo Kα
µ (mm1)4.29
Crystal size (mm)0.24 × 0.13 × 0.09
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.426, 0.699
No. of measured, independent and
observed [I > 2σ(I)] reflections
5163, 1860, 977
Rint0.080
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.068, 1.01
No. of reflections1860
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.52

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O30.821.832.549 (4)145.7
 

References

First citationBruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChung, J. G. (1999). Food Chem. Toxicol. 37, 327–334.  Web of Science CrossRef PubMed CAS Google Scholar
First citationLiu, C. Y., Wu, Y. Z., Zhou, D. X. & Wang, C. P. (2000). J. Biol. 17, 23–24.  CAS Google Scholar
First citationQi, J. S., Chao, Y. & Wang, Y. L. (2003). Chin. J. Appl. Chem. 20, 702–703.  CAS Google Scholar
First citationSheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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