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

Qing, W.-X.; Liu, Y.-Z.; Yao, S.-M.

doi:10.1107/S1600536809029067

organic compounds

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Volume 65| Part 8| August 2009| Page o2004

doi:10.1107/S1600536809029067

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

Wei-Xia Qing,^a Yan-Zhao Liu ^b and Su-Mei Yao ^a ^*

^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 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 ); Liu et al. (2000 ). For our work on the preparation of derivatives, see: Qi et al. (2003 ).

Experimental

Crystal data

C₉H₉BrO₃
M_r = 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 ) 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[F² > 2σ(F²)] = 0.045
wR(F²) = 0.068
S = 1.01
1860 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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.

Supporting information

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

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

checkCIF report

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 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].

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%).

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

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

C₉H₉BrO₃	F(000) = 488
M_r = 245.07	D_x = 1.710 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1164 reflections
a = 9.916 (3) Å	θ = 2.5–21.4°
b = 13.836 (5) Å	µ = 4.29 mm⁻¹
c = 6.940 (2) Å	T = 296 K
β = 90.031 (3)°	Needle-like, colourless
V = 952.0 (5) Å³	0.24 × 0.13 × 0.09 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1860 independent reflections
Radiation source: fine-focus sealed tube	977 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −12→9
T_min = 0.426, T_max = 0.699	k = −17→16
5163 measured reflections	l = −8→8

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.001P)²] where P = (F_o² + 2F_c²)/3
1860 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₉H₉BrO₃	V = 952.0 (5) Å³
M_r = 245.07	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.916 (3) Å	µ = 4.29 mm⁻¹
b = 13.836 (5) Å	T = 296 K
c = 6.940 (2) Å	0.24 × 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)
T_min = 0.426, T_max = 0.699	R_int = 0.080
5163 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.01	Δρ_max = 0.46 e Å⁻³
1860 reflections	Δρ_min = −0.52 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Br1	0.67087 (5)	0.52356 (3)	0.17229 (7)	0.0635 (2)
O1	1.0051 (3)	0.88085 (17)	0.2857 (4)	0.0522 (8)
H1A	1.0839	0.8682	0.3109	0.078*
O2	0.5841 (3)	0.7279 (2)	0.1634 (4)	0.0514 (8)
O3	1.2075 (3)	0.7721 (2)	0.3509 (4)	0.0625 (9)
C1	0.7770 (4)	0.6352 (3)	0.2110 (5)	0.0377 (11)
C2	0.9133 (4)	0.6264 (3)	0.2495 (5)	0.0398 (11)
H2A	0.9515	0.5651	0.2572	0.048*
C3	0.9948 (4)	0.7076 (3)	0.2771 (5)	0.0336 (10)
C4	0.9349 (4)	0.7981 (3)	0.2651 (5)	0.0379 (11)
C5	0.7969 (4)	0.8080 (3)	0.2272 (5)	0.0393 (11)
H5A	0.7584	0.8692	0.2200	0.047*
C6	0.7179 (4)	0.7270 (3)	0.2006 (5)	0.0382 (11)
C7	0.5177 (4)	0.8188 (3)	0.1589 (7)	0.0638 (14)
H7A	0.4238	0.8093	0.1308	0.096*
H7B	0.5575	0.8586	0.0610	0.096*
H7C	0.5269	0.8499	0.2819	0.096*
C8	1.1410 (5)	0.6994 (3)	0.3182 (6)	0.0445 (12)
C9	1.2063 (4)	0.6027 (3)	0.3192 (7)	0.0649 (14)
H9A	1.3005	0.6097	0.3482	0.097*
H9B	1.1962	0.5732	0.1948	0.097*
H9C	1.1645	0.5627	0.4151	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0606 (3)	0.0477 (3)	0.0823 (4)	−0.0137 (3)	−0.0044 (3)	−0.0034 (3)
O1	0.051 (2)	0.0372 (19)	0.069 (2)	−0.0123 (15)	0.0022 (16)	0.0005 (16)
O2	0.038 (2)	0.051 (2)	0.065 (2)	0.0066 (16)	−0.0004 (16)	0.0018 (16)
O3	0.043 (2)	0.068 (2)	0.077 (2)	−0.0145 (17)	−0.0017 (17)	−0.0097 (19)
C1	0.045 (3)	0.033 (3)	0.036 (3)	−0.003 (2)	0.005 (2)	0.002 (2)
C2	0.043 (3)	0.038 (3)	0.038 (3)	0.008 (2)	0.000 (2)	0.001 (2)
C3	0.035 (3)	0.035 (3)	0.030 (3)	0.001 (2)	−0.001 (2)	−0.002 (2)
C4	0.044 (3)	0.037 (3)	0.033 (3)	−0.009 (2)	0.010 (2)	0.001 (2)
C5	0.051 (3)	0.030 (3)	0.037 (3)	0.004 (2)	0.004 (2)	0.003 (2)
C6	0.035 (3)	0.048 (3)	0.031 (3)	0.003 (2)	0.007 (2)	−0.002 (2)
C7	0.037 (3)	0.081 (4)	0.074 (4)	0.015 (3)	0.001 (3)	0.008 (3)
C8	0.049 (3)	0.048 (3)	0.036 (3)	0.000 (3)	0.007 (2)	−0.004 (2)
C9	0.041 (3)	0.076 (4)	0.078 (4)	0.009 (3)	−0.016 (3)	−0.006 (3)

Geometric parameters (Å, º) top

Br1—C1	1.889 (4)	C3—C8	1.482 (5)
O1—C4	1.347 (4)	C4—C5	1.400 (5)
O1—H1A	0.8200	C5—C6	1.380 (5)
O2—C6	1.351 (4)	C5—H5A	0.9300
O2—C7	1.420 (4)	C7—H7A	0.9600
O3—C8	1.224 (4)	C7—H7B	0.9600
C1—C2	1.382 (5)	C7—H7C	0.9600
C1—C6	1.400 (5)	C8—C9	1.487 (5)
C2—C3	1.397 (5)	C9—H9A	0.9600
C2—H2A	0.9300	C9—H9B	0.9600
C3—C4	1.389 (5)	C9—H9C	0.9600

C4—O1—H1A	109.5	O2—C6—C1	115.5 (4)
C6—O2—C7	117.9 (3)	C5—C6—C1	119.4 (4)
C2—C1—C6	120.0 (4)	O2—C7—H7A	109.5
C2—C1—Br1	120.0 (3)	O2—C7—H7B	109.5
C6—C1—Br1	120.0 (3)	H7A—C7—H7B	109.5
C1—C2—C3	121.4 (4)	O2—C7—H7C	109.5
C1—C2—H2A	119.3	H7A—C7—H7C	109.5
C3—C2—H2A	119.3	H7B—C7—H7C	109.5
C4—C3—C2	118.0 (4)	O3—C8—C3	120.0 (4)
C4—C3—C8	119.9 (4)	O3—C8—C9	120.3 (4)
C2—C3—C8	122.1 (4)	C3—C8—C9	119.7 (4)
O1—C4—C3	122.6 (4)	C8—C9—H9A	109.5
O1—C4—C5	116.2 (4)	C8—C9—H9B	109.5
C3—C4—C5	121.1 (4)	H9A—C9—H9B	109.5
C6—C5—C4	120.0 (4)	C8—C9—H9C	109.5
C6—C5—H5A	120.0	H9A—C9—H9C	109.5
C4—C5—H5A	120.0	H9B—C9—H9C	109.5
O2—C6—C5	125.1 (4)

C6—C1—C2—C3	−0.5 (6)	C7—O2—C6—C1	177.5 (4)
Br1—C1—C2—C3	179.4 (3)	C4—C5—C6—O2	180.0 (3)
C1—C2—C3—C4	0.1 (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—O2	0.4 (5)
C8—C3—C4—O1	1.4 (5)	C2—C1—C6—C5	0.6 (6)
C2—C3—C4—C5	0.2 (5)	Br1—C1—C6—C5	−179.3 (3)
C8—C3—C4—C5	−179.8 (3)	C4—C3—C8—O3	3.6 (6)
O1—C4—C5—C6	178.8 (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—C9	3.7 (5)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₉H₉BrO₃
M_r	245.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.916 (3), 13.836 (5), 6.940 (2)
β (°)	90.031 (3)
V (Å³)	952.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.29
Crystal size (mm)	0.24 × 0.13 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.426, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	5163, 1860, 977
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.068, 1.01
No. of reflections	1860
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.82	1.83	2.549 (4)	145.7

References

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Chung, J. G. (1999). Food Chem. Toxicol. 37, 327–334. Web of Science CrossRef PubMed CAS Google Scholar
Liu, C. Y., Wu, Y. Z., Zhou, D. X. & Wang, C. P. (2000). J. Biol. 17, 23–24. CAS Google Scholar
Qi, J. S., Chao, Y. & Wang, Y. L. (2003). Chin. J. Appl. Chem. 20, 702–703. CAS Google Scholar
Sheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o2004

doi:10.1107/S1600536809029067

Open

access