Methyl 5-bromo-2-hy­droxy­benzoate

Abstract

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,

• a = 3.9829 (8) Å

• b = 9.0950 (19) Å

• c = 12.122 (3) Å

• β = 95.162 (9)°

• V = 437.33 (17) ų

• 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[F ² > 2σ(F ²)] = 0.058

• wR(F ²) = 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)

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812016297/hb6740Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

All H atoms were positioned with idealized geometry and were refined using a riding model with U_iso(H) = 1.2 or 1.5U_eq(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.

Figures

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.

Crystal data

C8H7BrO3	F(000) = 228
Mr = 231.04	Dx = 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

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

Refinement

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(Fo2) + (0.0687P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1644 reflections	Δρmax = 1.31 e Å−3
112 parameters	Δρmin = −0.72 e Å−3
1 restraint	Absolute structure: Flack (1983), 687 Freidel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.07 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.