Methyl 5-bromo-2-hy­droxy­benzoate

Mustafa, G.; Khan, I.U.; Ashiq, M.Z.; Akkurt, M.

doi:10.1107/S1600536812016297

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1467

doi:10.1107/S1600536812016297

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Methyl 5-bromo-2-hydroxybenzoate

Ghulam Mustafa,^a Islam Ullah Khan,^a Muhammad Zar Ashiq ^b and Mehmet Akkurt ^c ^*

^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 π–π 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 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₇BrO₃
M_r = 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 ) T_min = 0.228, T_max = 0.342
3242 measured reflections
1644 independent reflections
1186 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 1.31 e Å⁻³
Δρ_min = −0.72 e Å⁻³
Absolute structure: Flack (1983 ), 687 Freidel pairs
Flack parameter: 0.07 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812016297/hb6740sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016297/hb6740Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016297/hb6740Isup3.cml

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level.
	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

C₈H₇BrO₃	F(000) = 228
M_r = 231.04	D_x = 1.755 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1516 reflections
a = 3.9829 (8) Å	θ = 2.8–24.2°
b = 9.0950 (19) Å	µ = 4.66 mm⁻¹
c = 12.122 (3) Å	T = 296 K
β = 95.162 (9)°	Needle, yellow–brown
V = 437.33 (17) Å³	0.34 × 0.28 × 0.23 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1644 independent reflections
Radiation source: sealed tube	1186 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 26.5°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −4→4
T_min = 0.228, T_max = 0.342	k = −11→11
3242 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0687P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1644 reflections	Δρ_max = 1.31 e Å⁻³
112 parameters	Δρ_min = −0.72 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 687 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (3)

Crystal data top

C₈H₇BrO₃	V = 437.33 (17) Å³
M_r = 231.04	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 3.9829 (8) Å	µ = 4.66 mm⁻¹
b = 9.0950 (19) Å	T = 296 K
c = 12.122 (3) Å	0.34 × 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)
T_min = 0.228, T_max = 0.342	R_int = 0.057
3242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.142	Δρ_max = 1.31 e Å⁻³
S = 1.06	Δρ_min = −0.72 e Å⁻³
1644 reflections	Absolute structure: Flack (1983), 687 Freidel pairs
112 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
Br1	1.1035 (2)	1.05024 (13)	0.06707 (7)	0.0606 (3)
O1	0.663 (2)	0.7888 (8)	0.4895 (6)	0.076 (3)
O2	0.4780 (15)	0.5536 (9)	0.3653 (4)	0.0601 (18)
O3	0.6181 (14)	0.5492 (9)	0.1924 (4)	0.0512 (18)
C1	0.759 (2)	0.8434 (8)	0.3920 (6)	0.035 (3)
C2	0.901 (2)	0.9860 (8)	0.3906 (7)	0.043 (3)
C3	0.9992 (16)	1.0454 (12)	0.2961 (6)	0.042 (2)
C4	0.966 (2)	0.9673 (8)	0.1995 (7)	0.039 (3)
C5	0.8380 (19)	0.8249 (8)	0.1976 (6)	0.037 (3)
C6	0.736 (2)	0.7643 (7)	0.2943 (6)	0.033 (2)
C7	0.594 (2)	0.6113 (8)	0.2910 (7)	0.039 (3)
C8	0.478 (3)	0.4012 (8)	0.1801 (8)	0.060 (4)
H1	0.64600	0.85650	0.53340	0.1140*
H2	0.92750	1.04020	0.45590	0.0520*
H3	1.08960	1.13970	0.29710	0.0510*
H5	0.82060	0.77090	0.13220	0.0440*
H8A	0.59580	0.33700	0.23330	0.0910*
H8B	0.50350	0.36590	0.10670	0.0910*
H8C	0.24340	0.40340	0.19220	0.0910*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0692 (6)	0.0456 (4)	0.0687 (6)	−0.0185 (6)	0.0153 (4)	0.0107 (5)
O1	0.105 (6)	0.059 (4)	0.066 (4)	0.024 (4)	0.019 (4)	0.002 (3)
O2	0.096 (4)	0.034 (2)	0.054 (3)	−0.004 (5)	0.027 (3)	0.009 (4)
O3	0.070 (4)	0.030 (2)	0.055 (3)	−0.022 (4)	0.014 (2)	−0.006 (4)
C1	0.035 (5)	0.031 (4)	0.038 (4)	0.009 (3)	0.001 (3)	0.006 (3)
C2	0.051 (5)	0.031 (4)	0.047 (5)	0.005 (4)	−0.001 (4)	−0.009 (3)
C3	0.040 (4)	0.024 (3)	0.061 (5)	−0.004 (5)	−0.003 (3)	0.007 (6)
C4	0.035 (4)	0.029 (4)	0.052 (5)	0.000 (3)	0.003 (4)	0.009 (3)
C5	0.039 (5)	0.024 (3)	0.046 (5)	−0.001 (3)	−0.001 (3)	−0.001 (3)
C6	0.031 (4)	0.019 (3)	0.049 (5)	0.002 (3)	0.001 (3)	0.004 (3)
C7	0.039 (5)	0.028 (3)	0.050 (5)	0.003 (3)	−0.003 (4)	0.003 (4)
C8	0.078 (7)	0.016 (4)	0.087 (7)	−0.015 (4)	0.008 (5)	−0.005 (4)

Geometric parameters (Å, º) top

Br1—C4	1.899 (8)	C4—C5	1.391 (10)
O1—C1	1.368 (10)	C5—C6	1.389 (10)
O2—C7	1.173 (10)	C6—C7	1.501 (10)
O3—C7	1.333 (10)	C2—H2	0.9300
O3—C8	1.460 (11)	C3—H3	0.9300
O1—H1	0.8200	C5—H5	0.9300
C1—C6	1.382 (10)	C8—H8A	0.9600
C1—C2	1.416 (10)	C8—H8B	0.9600
C2—C3	1.356 (11)	C8—H8C	0.9600
C3—C4	1.366 (12)

C7—O3—C8	115.1 (7)	O3—C7—C6	111.1 (7)
C1—O1—H1	109.00	O2—C7—O3	124.3 (8)
O1—C1—C6	123.3 (7)	C1—C2—H2	119.00
C2—C1—C6	117.6 (7)	C3—C2—H2	119.00
O1—C1—C2	119.1 (7)	C2—C3—H3	120.00
C1—C2—C3	121.4 (8)	C4—C3—H3	120.00
C2—C3—C4	120.3 (9)	C4—C5—H5	120.00
Br1—C4—C5	119.3 (6)	C6—C5—H5	120.00
C3—C4—C5	120.4 (8)	O3—C8—H8A	109.00
Br1—C4—C3	120.4 (6)	O3—C8—H8B	109.00
C4—C5—C6	119.3 (7)	O3—C8—H8C	110.00
C1—C6—C7	120.1 (7)	H8A—C8—H8B	109.00
C5—C6—C7	118.9 (7)	H8A—C8—H8C	110.00
C1—C6—C5	121.0 (6)	H8B—C8—H8C	110.00
O2—C7—C6	124.6 (8)

C8—O3—C7—C6	−178.4 (7)	C2—C3—C4—C5	−1.4 (12)
C8—O3—C7—O2	1.8 (12)	Br1—C4—C5—C6	−179.7 (6)
C6—C1—C2—C3	2.5 (12)	C3—C4—C5—C6	1.7 (12)
O1—C1—C2—C3	−179.8 (8)	C4—C5—C6—C7	179.2 (7)
C2—C1—C6—C5	−2.2 (12)	C4—C5—C6—C1	0.2 (12)
C2—C1—C6—C7	178.8 (7)	C1—C6—C7—O2	4.8 (13)
O1—C1—C6—C5	−179.8 (8)	C5—C6—C7—O3	6.0 (10)
O1—C1—C6—C7	1.2 (12)	C1—C6—C7—O3	−174.9 (7)
C1—C2—C3—C4	−0.7 (12)	C5—C6—C7—O2	−174.2 (8)
C2—C3—C4—Br1	−180.0 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	2.25	3.065 (10)	170

Symmetry code: (i) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₇BrO₃
M_r	231.04
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	3.9829 (8), 9.0950 (19), 12.122 (3)
β (°)	95.162 (9)
V (Å³)	437.33 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.66
Crystal size (mm)	0.34 × 0.28 × 0.23

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.228, 0.342
No. of measured, independent and observed [I > 2σ(I)] reflections	3242, 1644, 1186
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.142, 1.06
No. of reflections	1644
No. of parameters	112
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.31, −0.72
Absolute structure	Flack (1983), 687 Freidel pairs
Absolute structure parameter	0.07 (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···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	2.25	3.065 (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

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