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

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ISSN: 2056-9890
Volume 68| Part 5| May 2012| Page o1467

Methyl 5-bromo-2-hy­dr­oxy­benzoate

aDepartment of Chemistry, GC University, Lahore 54000, Pakistan, bNational Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25000, Pakistan, and cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey
*Correspondence e-mail: akkurt@erciyes.edu.tr, gmustafa884@yahoo.com

(Received 14 April 2012; accepted 14 April 2012; online 21 April 2012)

The title compound, C8H7BrO3, is almost planar (r.m.s. deviation for the non-H atoms = 0.055 Å). In the crystal, O—H⋯O hydrogen bonds link the mol­ecules into C(6) chains propagating in [010]. Very weak aromatic ππ inter­actions [centroid–centroid distances = 3.984 (5) and 3.982 (5) Å] also occur.

Related literature

For the crystal structure of the methyl 4-bromo-3-hy­droxy­benzoate isomer, see: Huang et al. (2011[Huang, H.-R., Du, Z.-Y., Lu, Y.-J., Fang, Y.-X. & Zhang, K. (2011). Acta Cryst. E67, o115.]). For graph-set notation, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C8H7BrO3

  • Mr = 231.04

  • Monoclinic, P 21

  • a = 3.9829 (8) Å

  • b = 9.0950 (19) Å

  • c = 12.122 (3) Å

  • β = 95.162 (9)°

  • V = 437.33 (17) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 4.66 mm−1

  • T = 296 K

  • 0.34 × 0.28 × 0.23 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.228, Tmax = 0.342

  • 3242 measured reflections

  • 1644 independent reflections

  • 1186 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.058

  • wR(F2) = 0.142

  • S = 1.06

  • 1644 reflections

  • 112 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 1.31 e Å−3

  • Δρmin = −0.72 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 687 Freidel pairs

  • Flack parameter: 0.07 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O2i 0.82 2.25 3.065 (10) 170
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+1].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; 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: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON.

Supporting information


Comment top

In the title compound (I), (Fig. 1), all bond lengths and angles are comparable with those of its isomer methyl 4-bromo-3-hydroxybenzoate (Huang et al., 2011). These isomers crystallize in the monoclinic P 21 (Z= 2) and P 21/c (Z=4) space groups, respectively.

Both these crystals have two different supramolecular O—H···O hydrogen-bond patterns. In the crystal, molecules are linked by O—H···O hydrogen bonds (Table 1), forming a zigzag chain of C(6) motifs (Bernstein et al., 1995) along the [010] and are further interlinked through very weak π-π stacking interactions [centroid-centroid distances = 3.984 (5) and 3.982 (5) Å] between the benzene rings, along the [1 0 0] axis (Table 1 and Fig. 2).

Related literature top

For the crystal structure of the methyl 4-bromo-3-hydroxybenzoate isomer, see: Huang et al. (2011). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by dissolving methy-5-bromo-2-hydroxybenzoic acid (1.0 g, 4.6 mmol) in DMF (10 ml) and n-hexane washed sodium hydride (0.22 g, 9.0 mmol). The whole mixture was astirred at room temperature for 45 min followed by the addition of methyl iodide (0.85 g, 5.9 mmol). The whole reaction mixture was stirred at room temprature till the completion of the reaction and poured into crushed ice in a beaker. The pH of the mixture was adjusted to 4.0 with 1 N HCl. Precipitates were produced, filtered and washed twice with distilled water and crystallized from chloroform solution as yellow-brown needles.

Refinement top

All H atoms were positioned with idealized geometry and were refined using a riding model with Uiso(H) = 1.2 or 1.5Ueq(C) [O—H = 0.82 Å, C—H = 0.93 and 0.96 Å]. Four poorly fitted reflections (0 - 1 1), (-1 0 10), (0 1 1) and (1 6 3) were omitted from the refinement.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level.
[Figure 2] Fig. 2. View of the packing and hydrogen-bonding (dotted lines) of the title compound along the a axis.
Methyl 5-bromo-2-hydroxybenzoate top
Crystal data top
C8H7BrO3F(000) = 228
Mr = 231.04Dx = 1.755 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1516 reflections
a = 3.9829 (8) Åθ = 2.8–24.2°
b = 9.0950 (19) ŵ = 4.66 mm1
c = 12.122 (3) ÅT = 296 K
β = 95.162 (9)°Needle, yellow–brown
V = 437.33 (17) Å30.34 × 0.28 × 0.23 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
1644 independent reflections
Radiation source: sealed tube1186 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ϕ and ω scansθmax = 26.5°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 44
Tmin = 0.228, Tmax = 0.342k = 1111
3242 measured reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.142 w = 1/[σ2(Fo2) + (0.0687P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1644 reflectionsΔρmax = 1.31 e Å3
112 parametersΔρmin = 0.72 e Å3
1 restraintAbsolute structure: Flack (1983), 687 Freidel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.07 (3)
Crystal data top
C8H7BrO3V = 437.33 (17) Å3
Mr = 231.04Z = 2
Monoclinic, P21Mo Kα radiation
a = 3.9829 (8) ŵ = 4.66 mm1
b = 9.0950 (19) ÅT = 296 K
c = 12.122 (3) Å0.34 × 0.28 × 0.23 mm
β = 95.162 (9)°
Data collection top
Bruker APEXII CCD
diffractometer
1644 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
1186 reflections with I > 2σ(I)
Tmin = 0.228, Tmax = 0.342Rint = 0.057
3242 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.142Δρmax = 1.31 e Å3
S = 1.06Δρmin = 0.72 e Å3
1644 reflectionsAbsolute structure: Flack (1983), 687 Freidel pairs
112 parametersAbsolute structure parameter: 0.07 (3)
1 restraint
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Br11.1035 (2)1.05024 (13)0.06707 (7)0.0606 (3)
O10.663 (2)0.7888 (8)0.4895 (6)0.076 (3)
O20.4780 (15)0.5536 (9)0.3653 (4)0.0601 (18)
O30.6181 (14)0.5492 (9)0.1924 (4)0.0512 (18)
C10.759 (2)0.8434 (8)0.3920 (6)0.035 (3)
C20.901 (2)0.9860 (8)0.3906 (7)0.043 (3)
C30.9992 (16)1.0454 (12)0.2961 (6)0.042 (2)
C40.966 (2)0.9673 (8)0.1995 (7)0.039 (3)
C50.8380 (19)0.8249 (8)0.1976 (6)0.037 (3)
C60.736 (2)0.7643 (7)0.2943 (6)0.033 (2)
C70.594 (2)0.6113 (8)0.2910 (7)0.039 (3)
C80.478 (3)0.4012 (8)0.1801 (8)0.060 (4)
H10.646000.856500.533400.1140*
H20.927501.040200.455900.0520*
H31.089601.139700.297100.0510*
H50.820600.770900.132200.0440*
H8A0.595800.337000.233300.0910*
H8B0.503500.365900.106700.0910*
H8C0.243400.403400.192200.0910*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0692 (6)0.0456 (4)0.0687 (6)0.0185 (6)0.0153 (4)0.0107 (5)
O10.105 (6)0.059 (4)0.066 (4)0.024 (4)0.019 (4)0.002 (3)
O20.096 (4)0.034 (2)0.054 (3)0.004 (5)0.027 (3)0.009 (4)
O30.070 (4)0.030 (2)0.055 (3)0.022 (4)0.014 (2)0.006 (4)
C10.035 (5)0.031 (4)0.038 (4)0.009 (3)0.001 (3)0.006 (3)
C20.051 (5)0.031 (4)0.047 (5)0.005 (4)0.001 (4)0.009 (3)
C30.040 (4)0.024 (3)0.061 (5)0.004 (5)0.003 (3)0.007 (6)
C40.035 (4)0.029 (4)0.052 (5)0.000 (3)0.003 (4)0.009 (3)
C50.039 (5)0.024 (3)0.046 (5)0.001 (3)0.001 (3)0.001 (3)
C60.031 (4)0.019 (3)0.049 (5)0.002 (3)0.001 (3)0.004 (3)
C70.039 (5)0.028 (3)0.050 (5)0.003 (3)0.003 (4)0.003 (4)
C80.078 (7)0.016 (4)0.087 (7)0.015 (4)0.008 (5)0.005 (4)
Geometric parameters (Å, º) top
Br1—C41.899 (8)C4—C51.391 (10)
O1—C11.368 (10)C5—C61.389 (10)
O2—C71.173 (10)C6—C71.501 (10)
O3—C71.333 (10)C2—H20.9300
O3—C81.460 (11)C3—H30.9300
O1—H10.8200C5—H50.9300
C1—C61.382 (10)C8—H8A0.9600
C1—C21.416 (10)C8—H8B0.9600
C2—C31.356 (11)C8—H8C0.9600
C3—C41.366 (12)
C7—O3—C8115.1 (7)O3—C7—C6111.1 (7)
C1—O1—H1109.00O2—C7—O3124.3 (8)
O1—C1—C6123.3 (7)C1—C2—H2119.00
C2—C1—C6117.6 (7)C3—C2—H2119.00
O1—C1—C2119.1 (7)C2—C3—H3120.00
C1—C2—C3121.4 (8)C4—C3—H3120.00
C2—C3—C4120.3 (9)C4—C5—H5120.00
Br1—C4—C5119.3 (6)C6—C5—H5120.00
C3—C4—C5120.4 (8)O3—C8—H8A109.00
Br1—C4—C3120.4 (6)O3—C8—H8B109.00
C4—C5—C6119.3 (7)O3—C8—H8C110.00
C1—C6—C7120.1 (7)H8A—C8—H8B109.00
C5—C6—C7118.9 (7)H8A—C8—H8C110.00
C1—C6—C5121.0 (6)H8B—C8—H8C110.00
O2—C7—C6124.6 (8)
C8—O3—C7—C6178.4 (7)C2—C3—C4—C51.4 (12)
C8—O3—C7—O21.8 (12)Br1—C4—C5—C6179.7 (6)
C6—C1—C2—C32.5 (12)C3—C4—C5—C61.7 (12)
O1—C1—C2—C3179.8 (8)C4—C5—C6—C7179.2 (7)
C2—C1—C6—C52.2 (12)C4—C5—C6—C10.2 (12)
C2—C1—C6—C7178.8 (7)C1—C6—C7—O24.8 (13)
O1—C1—C6—C5179.8 (8)C5—C6—C7—O36.0 (10)
O1—C1—C6—C71.2 (12)C1—C6—C7—O3174.9 (7)
C1—C2—C3—C40.7 (12)C5—C6—C7—O2174.2 (8)
C2—C3—C4—Br1180.0 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.822.253.065 (10)170
Symmetry code: (i) x+1, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC8H7BrO3
Mr231.04
Crystal system, space groupMonoclinic, P21
Temperature (K)296
a, b, c (Å)3.9829 (8), 9.0950 (19), 12.122 (3)
β (°) 95.162 (9)
V3)437.33 (17)
Z2
Radiation typeMo Kα
µ (mm1)4.66
Crystal size (mm)0.34 × 0.28 × 0.23
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.228, 0.342
No. of measured, independent and
observed [I > 2σ(I)] reflections
3242, 1644, 1186
Rint0.057
(sin θ/λ)max1)0.628
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.142, 1.06
No. of reflections1644
No. of parameters112
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.31, 0.72
Absolute structureFlack (1983), 687 Freidel pairs
Absolute structure parameter0.07 (3)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.822.253.065 (10)170
Symmetry code: (i) x+1, y+1/2, z+1.
 

Acknowledgements

The authors are grateful to the Higher Education Commission (HEC), Pakistan, for financial support.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science
First citationBruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals
First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationHuang, H.-R., Du, Z.-Y., Lu, Y.-J., Fang, Y.-X. & Zhang, K. (2011). Acta Cryst. E67, o115.  Web of Science CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 5| May 2012| Page o1467
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