2,2-Dibromo-1-(4-hydr­oxy-3-methoxy­phen­yl)ethanone

Yang, X.-H.; Zhou, Y.-H.; Song, X.

doi:10.1107/S1600536809020650

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1489

doi:10.1107/S1600536809020650

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2,2-Dibromo-1-(4-hydroxy-3-methoxyphenyl)ethanone

Xiao-Hui Yang,^a Yong-Hong Zhou ^a ^* and Xing Song ^a

^aNational Engineering Laboratory for Biomass Chemical Utilization; Key and Open Laboratory of Forest Chemical Engineering SFA, Institute of Chemical Industry of Forest Products CAF, Nanjing 210042, People's Republic of China
^*Correspondence e-mail: yhzhou1966@yahoo.com.cn

(Received 24 May 2009; accepted 31 May 2009; online 6 June 2009)

The molecule of the title compound, C₉H₈Br₂O₃, is stabilized by an intramolecular O—H⋯O interaction. Intermolecular C—H⋯O interactions connect molecules into a two-dimensional array in the bc plane; connections between these are afforded by π–π stacking interactions [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_r = 323.97
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.067
wR(F²) = 0.159
S = 0.96
1900 reflections
127 parameters
61 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.65 e Å⁻³

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) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

Lignin is natural polymer occurring in plant cell walls and is considered to be the second most abundant biopolymer after cellulose. The beta-O-4 structure is the most abundant substructure in lignin (Cathala et al., 2003). In order to prepare well defined linear polymers composed of the β-O-4 structure and in attempt to develop new utilization methods of lignins (Kishimoto et al., 2005), a new compound, 2,2-dibromo-1-(4-hydroxy-3-methoxyphenyl)ethanone, (I), was synthesized and its structure determined using single-crystal X-ray methods.

The molecular conformation of (I), Fig. 1, is stabilized by an intramolecular O—H···O interaction formed between the hydroxyl-H and methoxy-O atoms (H···O = 2.27 Å). The molecules are connected into a 2-D array via C-H···O interactions in the bc-plane (Table 1). Connections between the layers are afforded by π-π stacking interactions, with the shortest centroid···centroid distance being 3.596 (5)Å.

Related literature top

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 top

To a stirred solution of acetovanillone (5 g, 0.03 mol) in anhydrous CHCl₃, bromine (3.1 ml, 0.06 mol) was added dropwise under nitrogen over 2 h at 273 K. The reaction mixture was kept at 273k for 1 h. The reaction mixture was diluted with ether and washed with ice-cold water and brine. The solution was dried over anhydrous Na₂SO₄ and concentrated to dryness in vacuo. The crude crystalline product was purified by column chromatography to obtain a pure white solid, (I). Colourless single crystals were grown by slow evaporation of an ethyl acetate solution of (I).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.

(I) top

Crystal data top

C₉H₈Br₂O₃	F(000) = 624
M_r = 323.97	D_x = 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

Data collection top

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

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0723P)²] where P = (F_o² + 2F_c²)/3
1900 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.56 e Å⁻³
61 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

C₉H₈Br₂O₃	V = 1042.3 (4) Å³
M_r = 323.97	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0370 (14) Å	µ = 7.76 mm⁻¹
b = 10.805 (2) Å	T = 295 K
c = 13.871 (3) Å	0.10 × 0.05 × 0.05 mm
β = 98.80 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	894 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.041
T_min = 0.511, T_max = 0.698	3 standard reflections every 200 reflections
2060 measured reflections	intensity decay: 1%
1900 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	61 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 0.96	Δρ_max = 0.56 e Å⁻³
1900 reflections	Δρ_min = −0.65 e Å⁻³
127 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	0.08467 (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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y+1/2, −z−1/2; (ii) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈Br₂O₃
M_r	323.97
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.0370 (14), 10.805 (2), 13.871 (3)
β (°)	98.80 (3)
V (Å³)	1042.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.76
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.511, 0.698
No. of measured, independent and observed [I > 2σ(I)] reflections	2060, 1900, 894
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.159, 0.96
No. of reflections	1900
No. of parameters	127
No. of restraints	61
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.65

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y+1/2, −z−1/2; (ii) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2005B04) for support.

References

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