2,2-Dibromo-1-(4-hydr-oxy-3-methoxy-phen-yl)ethanone.

The mol-ecule of the title compound, C(9)H(8)Br(2)O(3), is stabilized by an intra-molecular O-H⋯O inter-action. Inter-molecular C-H⋯O inter-actions connect mol-ecules into a two-dimensional array in the bc plane; connections between these are afforded by π-π stacking inter-actions [centroid-centroid distance 3.596 (5) Å].

Related literature

For the beta-O-4 substructure in lignin, see: Cathala et al. (2003 ▶). For attempts to prepare well defined linear polymers with the β-O-4 structure and to develop new methods of utilizing lignins, see: Kishimoto et al. (2005 ▶).

Experimental

Crystal data

C9H8Br2O3

M = 323.97

Monoclinic,

a = 7.0370 (14) Å

b = 10.805 (2) Å

c = 13.871 (3) Å

β = 98.80 (3)°

V = 1042.3 (4) Å3

Z = 4

Mo Kα radiation

μ = 7.76 mm−1

T = 295 K

0.10 × 0.05 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.511, T max = 0.698

2060 measured reflections

1900 independent reflections

894 reflections with I > 2σ(I)

R int = 0.041

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.067

wR(F 2) = 0.159

S = 0.96

1900 reflections

127 parameters

61 restraints

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.65 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks qj0709, I. DOI: 10.1107/S1600536809020650/tk2463sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020650/tk2463Isup2.hkl

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

C9H8Br2O3	F(000) = 624
Mr = 323.97	Dx = 2.065 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.0370 (14) Å	θ = 10–13°
b = 10.805 (2) Å	µ = 7.76 mm−1
c = 13.871 (3) Å	T = 295 K
β = 98.80 (3)°	Needle, colourless
V = 1042.3 (4) Å3	0.10 × 0.05 × 0.05 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	894 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
graphite	θmax = 25.3°, θmin = 2.4°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.511, Tmax = 0.698	l = −16→16
2060 measured reflections	3 standard reflections every 200 reflections
1900 independent reflections	intensity decay: 1%

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159	H-atom parameters constrained
S = 0.96	w = 1/[σ2(Fo2) + (0.0723P)2] where P = (Fo2 + 2Fc2)/3
1900 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.56 e Å−3
61 restraints	Δρmin = −0.65 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.08467 (19)	0.97920 (12)	0.38634 (8)	0.0775 (5)
Br2	0.51183 (19)	0.91674 (13)	0.35768 (10)	0.0890 (5)
O1	0.1990 (9)	1.1174 (7)	−0.1321 (4)	0.0521 (17)
O2	0.2770 (9)	0.8866 (7)	−0.1677 (4)	0.062 (2)
H2A	0.2526	0.9407	−0.2123	0.074*
O3	0.2364 (10)	1.1382 (6)	0.2363 (4)	0.0578 (19)
C1	0.1731 (15)	1.2472 (10)	−0.1180 (7)	0.065 (3)
H1A	0.1408	1.2869	−0.1802	0.097*
H1B	0.2900	1.2820	−0.0840	0.097*
H1C	0.0712	1.2596	−0.0802	0.097*
C2	0.2291 (13)	1.0450 (8)	−0.0514 (6)	0.041 (2)
C3	0.2247 (12)	1.0754 (8)	0.0407 (5)	0.036 (2)
H3A	0.2002	1.1572	0.0554	0.043*
C4	0.2555 (12)	0.9894 (8)	0.1168 (5)	0.0303 (19)
C5	0.2965 (12)	0.8669 (8)	0.0924 (5)	0.037 (2)
H5A	0.3198	0.8071	0.1410	0.045*
C6	0.3021 (13)	0.8348 (9)	−0.0047 (6)	0.043 (2)
H6A	0.3279	0.7536	−0.0208	0.052*
C7	0.2714 (13)	0.9187 (9)	−0.0728 (6)	0.044 (2)
C8	0.2469 (13)	1.0318 (9)	0.2175 (6)	0.039 (2)
C9	0.2485 (13)	0.9338 (9)	0.2920 (6)	0.048 (2)
H9A	0.2046	0.8555	0.2606	0.057*

	U11	U22	U33	U12	U13	U23
Br1	0.0952 (10)	0.0694 (9)	0.0809 (7)	0.0149 (8)	0.0546 (7)	0.0129 (7)
Br2	0.0631 (8)	0.0828 (11)	0.1166 (10)	0.0081 (8)	−0.0004 (7)	0.0338 (8)
O1	0.051 (4)	0.059 (5)	0.046 (3)	−0.001 (4)	0.008 (3)	0.009 (3)
O2	0.065 (5)	0.072 (5)	0.055 (4)	0.001 (4)	0.030 (3)	−0.003 (4)
O3	0.105 (6)	0.018 (4)	0.058 (4)	0.001 (4)	0.037 (4)	−0.001 (3)
C1	0.072 (8)	0.055 (8)	0.068 (7)	−0.007 (7)	0.017 (6)	0.020 (6)
C2	0.044 (5)	0.035 (5)	0.045 (4)	−0.001 (4)	0.009 (4)	0.003 (4)
C3	0.041 (5)	0.020 (4)	0.048 (4)	−0.006 (4)	0.013 (4)	0.000 (3)
C4	0.027 (4)	0.024 (4)	0.040 (3)	−0.003 (4)	0.006 (3)	0.000 (3)
C5	0.038 (5)	0.031 (4)	0.041 (4)	0.004 (4)	−0.002 (4)	0.001 (4)
C6	0.046 (5)	0.034 (5)	0.052 (4)	0.000 (4)	0.015 (4)	−0.005 (4)
C7	0.046 (5)	0.048 (5)	0.045 (4)	0.002 (5)	0.025 (4)	−0.005 (4)
C8	0.042 (5)	0.025 (5)	0.053 (4)	0.004 (4)	0.019 (4)	0.001 (4)
C9	0.049 (5)	0.033 (5)	0.064 (5)	−0.002 (5)	0.015 (4)	0.004 (4)

Br1—C9	1.935 (9)	C2—C7	1.437 (12)
Br2—C9	1.945 (9)	C3—C4	1.398 (10)
O1—C2	1.355 (10)	C3—H3A	0.9300
O1—C1	1.431 (12)	C4—C5	1.407 (11)
O2—C7	1.369 (9)	C4—C8	1.481 (11)
O2—H2A	0.8500	C5—C6	1.398 (11)
O3—C8	1.184 (10)	C5—H5A	0.9300
C1—H1A	0.9600	C6—C7	1.302 (11)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C8—C9	1.478 (12)
C2—C3	1.324 (11)	C9—H9A	0.9800
C2—O1—C1	117.4 (7)	C6—C5—H5A	119.9
C7—O2—H2A	119.6	C4—C5—H5A	119.9
O1—C1—H1A	109.5	C7—C6—C5	120.0 (9)
O1—C1—H1B	109.5	C7—C6—H6A	120.0
H1A—C1—H1B	109.5	C5—C6—H6A	120.0
O1—C1—H1C	109.5	C6—C7—O2	119.7 (9)
H1A—C1—H1C	109.5	C6—C7—C2	121.9 (8)
H1B—C1—H1C	109.5	O2—C7—C2	118.4 (8)
C3—C2—O1	129.0 (9)	O3—C8—C9	122.4 (8)
C3—C2—C7	118.0 (8)	O3—C8—C4	121.4 (8)
O1—C2—C7	112.9 (7)	C9—C8—C4	116.2 (8)
C2—C3—C4	122.7 (8)	C8—C9—Br1	110.5 (6)
C2—C3—H3A	118.7	C8—C9—Br2	107.5 (6)
C4—C3—H3A	118.7	Br1—C9—Br2	109.3 (4)
C3—C4—C5	117.2 (7)	C8—C9—H9A	109.8
C3—C4—C8	118.9 (7)	Br1—C9—H9A	109.8
C5—C4—C8	123.9 (7)	Br2—C9—H9A	109.8
C6—C5—C4	120.1 (8)
C1—O1—C2—C3	5.5 (14)	O1—C2—C7—C6	−179.1 (8)
C1—O1—C2—C7	−174.4 (8)	C3—C2—C7—O2	−179.7 (9)
O1—C2—C3—C4	178.7 (8)	O1—C2—C7—O2	0.2 (12)
C7—C2—C3—C4	−1.3 (13)	C3—C4—C8—O3	−8.6 (13)
C2—C3—C4—C5	1.4 (13)	C5—C4—C8—O3	170.2 (9)
C2—C3—C4—C8	−179.7 (9)	C3—C4—C8—C9	170.2 (8)
C3—C4—C5—C6	−1.0 (12)	C5—C4—C8—C9	−10.9 (12)
C8—C4—C5—C6	−179.8 (8)	O3—C8—C9—Br1	35.2 (12)
C4—C5—C6—C7	0.7 (14)	C4—C8—C9—Br1	−143.6 (7)
C5—C6—C7—O2	−179.9 (8)	O3—C8—C9—Br2	−84.0 (10)
C5—C6—C7—C2	−0.7 (14)	C4—C8—C9—Br2	97.2 (8)
C3—C2—C7—C6	1.0 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.85	2.27	2.617 (11)	105
C1—H1A···O2i	0.96	2.51	3.398 (11)	153
C5—H5A···O3ii	0.93	2.57	3.460 (10)	161
C9—H9A···O3ii	0.98	2.38	3.222 (11)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1	0.85	2.27	2.617 (11)	105
C1—H1A⋯O2i	0.96	2.51	3.398 (11)	153
C5—H5A⋯O3ii	0.93	2.57	3.460 (10)	161
C9—H9A⋯O3ii	0.98	2.38	3.222 (11)	143

Symmetry codes: (i) ; (ii) .