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

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ISSN: 2056-9890

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

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 ππ stacking inter­actions [centroid–centroid distance 3.596 (5) Å].

Related literature

For the beta-O-4 substructure in lignin, see: Cathala et al. (2003[Cathala, B., Saake, B., Faix, O. & Monties, B. (2003). J. Chromatogr. A, 1020, 229-239.]). 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[Kishimoto, T., Uraki, Y. & Ubukata, M. (2005). Org. Biomol. Chem. 3, 1067-1073.]).

[Scheme 1]

Experimental

Crystal data
  • C9H8Br2O3

  • Mr = 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[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.511, Tmax = 0.698

  • 2060 measured reflections

  • 1900 independent reflections

  • 894 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.65 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Enraf-Nonius (1994). CAD-4 EXPRESS. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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).

Refinement top

H atoms were placed in calculated positions and treated using a riding model, with C—H = 0.93–0.98 Å and O—H = 0.85 Å, and with Uiso(H) = 1.2Ueq(C, O) or 1.5Ueq(C) for methyl-H atoms.

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
[Figure 1] 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
C9H8Br2O3F(000) = 624
Mr = 323.97Dx = 2.065 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 7.0370 (14) Åθ = 10–13°
b = 10.805 (2) ŵ = 7.76 mm1
c = 13.871 (3) ÅT = 295 K
β = 98.80 (3)°Needle, colourless
V = 1042.3 (4) Å30.10 × 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 tubeRint = 0.041
Graphite monochromatorθmax = 25.3°, θmin = 2.4°
ω/2θ scansh = 08
Absorption correction: ψ scan
(North et al., 1968)
k = 012
Tmin = 0.511, Tmax = 0.698l = 1616
2060 measured reflections3 standard reflections every 200 reflections
1900 independent reflections intensity decay: 1%
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)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-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 parametersΔρmax = 0.56 e Å3
61 restraintsΔρmin = 0.65 e Å3
Crystal data top
C9H8Br2O3V = 1042.3 (4) Å3
Mr = 323.97Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.0370 (14) ŵ = 7.76 mm1
b = 10.805 (2) ÅT = 295 K
c = 13.871 (3) Å0.10 × 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)
Rint = 0.041
Tmin = 0.511, Tmax = 0.6983 standard reflections every 200 reflections
2060 measured reflections intensity decay: 1%
1900 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06761 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 0.96Δρmax = 0.56 e Å3
1900 reflectionsΔρmin = 0.65 e Å3
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
xyzUiso*/Ueq
Br10.08467 (19)0.97920 (12)0.38634 (8)0.0775 (5)
Br20.51183 (19)0.91674 (13)0.35768 (10)0.0890 (5)
O10.1990 (9)1.1174 (7)0.1321 (4)0.0521 (17)
O20.2770 (9)0.8866 (7)0.1677 (4)0.062 (2)
H2A0.25260.94070.21230.074*
O30.2364 (10)1.1382 (6)0.2363 (4)0.0578 (19)
C10.1731 (15)1.2472 (10)0.1180 (7)0.065 (3)
H1A0.14081.28690.18020.097*
H1B0.29001.28200.08400.097*
H1C0.07121.25960.08020.097*
C20.2291 (13)1.0450 (8)0.0514 (6)0.041 (2)
C30.2247 (12)1.0754 (8)0.0407 (5)0.036 (2)
H3A0.20021.15720.05540.043*
C40.2555 (12)0.9894 (8)0.1168 (5)0.0303 (19)
C50.2965 (12)0.8669 (8)0.0924 (5)0.037 (2)
H5A0.31980.80710.14100.045*
C60.3021 (13)0.8348 (9)0.0047 (6)0.043 (2)
H6A0.32790.75360.02080.052*
C70.2714 (13)0.9187 (9)0.0728 (6)0.044 (2)
C80.2469 (13)1.0318 (9)0.2175 (6)0.039 (2)
C90.2485 (13)0.9338 (9)0.2920 (6)0.048 (2)
H9A0.20460.85550.26060.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0952 (10)0.0694 (9)0.0809 (7)0.0149 (8)0.0546 (7)0.0129 (7)
Br20.0631 (8)0.0828 (11)0.1166 (10)0.0081 (8)0.0004 (7)0.0338 (8)
O10.051 (4)0.059 (5)0.046 (3)0.001 (4)0.008 (3)0.009 (3)
O20.065 (5)0.072 (5)0.055 (4)0.001 (4)0.030 (3)0.003 (4)
O30.105 (6)0.018 (4)0.058 (4)0.001 (4)0.037 (4)0.001 (3)
C10.072 (8)0.055 (8)0.068 (7)0.007 (7)0.017 (6)0.020 (6)
C20.044 (5)0.035 (5)0.045 (4)0.001 (4)0.009 (4)0.003 (4)
C30.041 (5)0.020 (4)0.048 (4)0.006 (4)0.013 (4)0.000 (3)
C40.027 (4)0.024 (4)0.040 (3)0.003 (4)0.006 (3)0.000 (3)
C50.038 (5)0.031 (4)0.041 (4)0.004 (4)0.002 (4)0.001 (4)
C60.046 (5)0.034 (5)0.052 (4)0.000 (4)0.015 (4)0.005 (4)
C70.046 (5)0.048 (5)0.045 (4)0.002 (5)0.025 (4)0.005 (4)
C80.042 (5)0.025 (5)0.053 (4)0.004 (4)0.019 (4)0.001 (4)
C90.049 (5)0.033 (5)0.064 (5)0.002 (5)0.015 (4)0.004 (4)
Geometric parameters (Å, º) top
Br1—C91.935 (9)C2—C71.437 (12)
Br2—C91.945 (9)C3—C41.398 (10)
O1—C21.355 (10)C3—H3A0.9300
O1—C11.431 (12)C4—C51.407 (11)
O2—C71.369 (9)C4—C81.481 (11)
O2—H2A0.8500C5—C61.398 (11)
O3—C81.184 (10)C5—H5A0.9300
C1—H1A0.9600C6—C71.302 (11)
C1—H1B0.9600C6—H6A0.9300
C1—H1C0.9600C8—C91.478 (12)
C2—C31.324 (11)C9—H9A0.9800
C2—O1—C1117.4 (7)C6—C5—H5A119.9
C7—O2—H2A119.6C4—C5—H5A119.9
O1—C1—H1A109.5C7—C6—C5120.0 (9)
O1—C1—H1B109.5C7—C6—H6A120.0
H1A—C1—H1B109.5C5—C6—H6A120.0
O1—C1—H1C109.5C6—C7—O2119.7 (9)
H1A—C1—H1C109.5C6—C7—C2121.9 (8)
H1B—C1—H1C109.5O2—C7—C2118.4 (8)
C3—C2—O1129.0 (9)O3—C8—C9122.4 (8)
C3—C2—C7118.0 (8)O3—C8—C4121.4 (8)
O1—C2—C7112.9 (7)C9—C8—C4116.2 (8)
C2—C3—C4122.7 (8)C8—C9—Br1110.5 (6)
C2—C3—H3A118.7C8—C9—Br2107.5 (6)
C4—C3—H3A118.7Br1—C9—Br2109.3 (4)
C3—C4—C5117.2 (7)C8—C9—H9A109.8
C3—C4—C8118.9 (7)Br1—C9—H9A109.8
C5—C4—C8123.9 (7)Br2—C9—H9A109.8
C6—C5—C4120.1 (8)
C1—O1—C2—C35.5 (14)O1—C2—C7—C6179.1 (8)
C1—O1—C2—C7174.4 (8)C3—C2—C7—O2179.7 (9)
O1—C2—C3—C4178.7 (8)O1—C2—C7—O20.2 (12)
C7—C2—C3—C41.3 (13)C3—C4—C8—O38.6 (13)
C2—C3—C4—C51.4 (13)C5—C4—C8—O3170.2 (9)
C2—C3—C4—C8179.7 (9)C3—C4—C8—C9170.2 (8)
C3—C4—C5—C61.0 (12)C5—C4—C8—C910.9 (12)
C8—C4—C5—C6179.8 (8)O3—C8—C9—Br135.2 (12)
C4—C5—C6—C70.7 (14)C4—C8—C9—Br1143.6 (7)
C5—C6—C7—O2179.9 (8)O3—C8—C9—Br284.0 (10)
C5—C6—C7—C20.7 (14)C4—C8—C9—Br297.2 (8)
C3—C2—C7—C61.0 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2A···O10.852.272.617 (11)105
C1—H1A···O2i0.962.513.398 (11)153
C5—H5A···O3ii0.932.573.460 (10)161
C9—H9A···O3ii0.982.383.222 (11)143
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC9H8Br2O3
Mr323.97
Crystal system, space groupMonoclinic, P21/n
Temperature (K)295
a, b, c (Å)7.0370 (14), 10.805 (2), 13.871 (3)
β (°) 98.80 (3)
V3)1042.3 (4)
Z4
Radiation typeMo Kα
µ (mm1)7.76
Crystal size (mm)0.10 × 0.05 × 0.05
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.511, 0.698
No. of measured, independent and
observed [I > 2σ(I)] reflections
2060, 1900, 894
Rint0.041
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.159, 0.96
No. of reflections1900
No. of parameters127
No. of restraints61
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O2—H2A···O10.852.272.617 (11)105
C1—H1A···O2i0.962.513.398 (11)153
C5—H5A···O3ii0.932.573.460 (10)161
C9—H9A···O3ii0.982.383.222 (11)143
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y1/2, z+1/2.
 

Acknowledgements

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

References

First citationCathala, B., Saake, B., Faix, O. & Monties, B. (2003). J. Chromatogr. A, 1020, 229–239.  Web of Science CrossRef PubMed CAS Google Scholar
First citationEnraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationKishimoto, T., Uraki, Y. & Ubukata, M. (2005). Org. Biomol. Chem. 3, 1067–1073.  Web of Science CrossRef PubMed CAS Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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COMMUNICATIONS
ISSN: 2056-9890
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