Methyl 4-bromo-3-hy­droxy­benzoate

Huang, H.-R.; Du, Z.-Y.; Lu, Y.-J.; Fang, Y.-X.; Zhang, K.

doi:10.1107/S1600536810051445

organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o115

https://doi.org/10.1107/S1600536810051445

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Methyl 4-bromo-3-hydroxybenzoate

Hua-Rong Huang,^a ^* Zhi-Yun Du,^a Yu-Jing Lu,^a Yan-Xiong Fang ^a and Kun Zhang ^a

^aGuangdong University of Technology, Faculty of Chemical Engineering and Light Industry, Guangzhou 510006, Guangdong, People's Republic of China
^*Correspondence e-mail: corihhr@yahoo.cn

(Received 25 November 2010; accepted 8 December 2010; online 11 December 2010)

In the title compound, C₈H₇BrO₃, the methoxycarbonyl group is twisted at a dihedral angle of 8.06 (4)° with respect to the benzene ring. In the crystal, molecules are connected by O—H⋯O hydrogen bonds into helical chains running along the b axis.

Related literature

For applications of methyl 3-hydroxybenzoate derivatives in the synthesis of various broad-spectrum antimicrobials, see: Zhong et al. (2001 ). For the synthesis of the title compound, see: Nie et al. (2005 ).

Experimental

Crystal data

C₈H₇BrO₃
M_r = 231.05
Monoclinic, P 2₁ /c
a = 10.812 (4) Å
b = 6.317 (2) Å
c = 12.490 (5) Å
β = 100.164 (6)°
V = 839.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 4.86 mm⁻¹
T = 293 K
0.27 × 0.24 × 0.16 mm

Data collection

Bruker SMART CCD 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.354, T_max = 0.511
4755 measured reflections
1831 independent reflections
1129 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.172
S = 1.08
1831 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.87	2.681 (7)	170
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; 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 global, I. DOI: https://doi.org/10.1107/S1600536810051445/xu5110sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051445/xu5110Isup2.hkl

checkCIF report

Comment top

The methyl 3-hydroxybenzoate derivatives as important starting materials have been applied to synthesis various broad-spectrum antimicrobials (Nie et al., 2005) and design cryptophane derivatives in self-assembling of supermolecular chemistry (Zhong et al., 2001). Here we report the structure of the title compound (Fig. 1).

In the crystal structure of the title compound, there are linked by an intermolecular O-H···O hydrogen bond between hydroxyl and carbonyl groups forming an infinite helical chain along the b axis (Table 1 and Fig. 2). And no significant interaction is observed between the chains.

Related literature top

For applications of methyl 3-hydroxybenzoate derivatives in the synthesis of various broad-spectrum antimicrobials, see: Zhong et al. (2001). For the synthesis of the title compound, see: Nie et al. (2005).

Experimental top

The title compound was synthesized as previously reported (Nie et al., 2005). The electrospray ionization mass spectrum (ESI-MS) showed an intense peak of molecular ions at m/z 230. Single crystals suitable for X-ray diffraction were obtained from methanol solution in room temperature.

Structure description top

For applications of methyl 3-hydroxybenzoate derivatives in the synthesis of various broad-spectrum antimicrobials, see: Zhong et al. (2001). For the synthesis of the title compound, see: Nie et al. (2005).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999; 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. Title molecule showing the 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing of the title compound as viewed along the b axis. Dashed lines indicate helical hydrogen-bonding chain Symmetry: A = -x + 1, y + 1/2, -z+1.5; B = -x + 1, y - 1/2, -z+1.5.

Methyl 4-bromo-3-hydroxybenzoate top

Crystal data top

C₈H₇BrO₃	F(000) = 456
M_r = 231.05	D_x = 1.828 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1334 reflections
a = 10.812 (4) Å	θ = 2.3–24.2°
b = 6.317 (2) Å	µ = 4.86 mm⁻¹
c = 12.490 (5) Å	T = 293 K
β = 100.164 (6)°	Plate, colorless
V = 839.7 (5) Å³	0.27 × 0.24 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD 1000 diffractometer	1831 independent reflections
Radiation source: fine-focus sealed tube	1129 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.2°, θ_min = 1.9°
φ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→3
T_min = 0.354, T_max = 0.511	l = −15→16
4755 measured reflections

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)] = 0.058	Hydrogen site location: difference Fourier map
wR(F²) = 0.172	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0685P)² + 2.8188P] where P = (F_o² + 2F_c²)/3
1831 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₈H₇BrO₃	V = 839.7 (5) Å³
M_r = 231.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.812 (4) Å	µ = 4.86 mm⁻¹
b = 6.317 (2) Å	T = 293 K
c = 12.490 (5) Å	0.27 × 0.24 × 0.16 mm
β = 100.164 (6)°

Data collection top

Bruker SMART CCD 1000 diffractometer	1831 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1129 reflections with I > 2σ(I)
T_min = 0.354, T_max = 0.511	R_int = 0.042
4755 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.08	Δρ_max = 0.46 e Å⁻³
1831 reflections	Δρ_min = −0.55 e Å⁻³
111 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.92070 (8)	1.12616 (14)	0.78430 (7)	0.0617 (4)
C1	0.8397 (6)	0.8935 (11)	0.8349 (5)	0.0392 (15)
C2	0.7180 (6)	0.8391 (11)	0.7823 (5)	0.0382 (15)
C3	0.6621 (5)	0.6667 (10)	0.8204 (5)	0.0357 (15)
H3	0.5809	0.6296	0.7877	0.043*
C4	0.7238 (6)	0.5454 (10)	0.9072 (5)	0.0331 (14)
C5	0.8426 (6)	0.6045 (11)	0.9592 (5)	0.0425 (16)
H5	0.8837	0.5274	1.0183	0.051*
C6	0.8996 (6)	0.7797 (12)	0.9223 (6)	0.0449 (17)
H6	0.9792	0.8206	0.9571	0.054*
C7	0.6617 (6)	0.3570 (10)	0.9440 (5)	0.0396 (15)
C8	0.6834 (8)	0.0661 (13)	1.0640 (6)	0.057 (2)
H8A	0.6194	0.1164	1.1020	0.086*
H8B	0.7478	−0.0043	1.1142	0.086*
H8C	0.6471	−0.0314	1.0082	0.086*
O1	0.6635 (5)	0.9620 (9)	0.6988 (4)	0.0565 (14)
H1	0.5947	0.9128	0.6724	0.085*
O2	0.5536 (5)	0.3093 (9)	0.9112 (4)	0.0589 (15)
O3	0.7379 (4)	0.2443 (7)	1.0147 (4)	0.0432 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0603 (5)	0.0604 (6)	0.0619 (5)	−0.0167 (4)	0.0043 (4)	0.0095 (4)
C1	0.037 (3)	0.039 (4)	0.041 (3)	−0.006 (3)	0.006 (3)	−0.002 (3)
C2	0.037 (3)	0.043 (4)	0.033 (3)	0.003 (3)	0.003 (3)	−0.001 (3)
C3	0.026 (3)	0.043 (4)	0.037 (3)	−0.004 (3)	−0.001 (2)	−0.006 (3)
C4	0.033 (3)	0.035 (3)	0.030 (3)	−0.002 (3)	0.001 (3)	−0.003 (3)
C5	0.041 (4)	0.038 (4)	0.044 (4)	0.004 (3)	−0.008 (3)	−0.004 (3)
C6	0.037 (4)	0.043 (4)	0.050 (4)	−0.009 (3)	−0.003 (3)	−0.005 (3)
C7	0.045 (4)	0.036 (4)	0.037 (3)	−0.002 (3)	0.006 (3)	−0.005 (3)
C8	0.072 (5)	0.051 (5)	0.049 (4)	0.003 (4)	0.009 (4)	0.006 (4)
O1	0.050 (3)	0.057 (3)	0.055 (3)	−0.008 (3)	−0.011 (2)	0.022 (3)
O2	0.040 (3)	0.057 (3)	0.072 (3)	−0.014 (2)	−0.011 (2)	0.014 (3)
O3	0.044 (3)	0.037 (3)	0.044 (3)	−0.005 (2)	−0.003 (2)	0.009 (2)

Geometric parameters (Å, º) top

Br1—C1	1.876 (7)	C5—H5	0.9300
C1—C6	1.370 (10)	C6—H6	0.9300
C1—C2	1.406 (9)	C7—O2	1.206 (8)
C2—O1	1.349 (8)	C7—O3	1.307 (8)
C2—C3	1.371 (9)	C8—O3	1.457 (9)
C3—C4	1.397 (9)	C8—H8A	0.9600
C3—H3	0.9300	C8—H8B	0.9600
C4—C5	1.384 (9)	C8—H8C	0.9600
C4—C7	1.480 (9)	O1—H1	0.8200
C5—C6	1.385 (10)

C6—C1—C2	121.0 (6)	C1—C6—C5	120.6 (6)
C6—C1—Br1	119.8 (5)	C1—C6—H6	119.7
C2—C1—Br1	119.2 (5)	C5—C6—H6	119.7
O1—C2—C3	124.5 (6)	O2—C7—O3	123.5 (6)
O1—C2—C1	117.7 (6)	O2—C7—C4	124.1 (6)
C3—C2—C1	117.7 (6)	O3—C7—C4	112.4 (5)
C2—C3—C4	121.7 (6)	O3—C8—H8A	109.5
C2—C3—H3	119.1	O3—C8—H8B	109.5
C4—C3—H3	119.1	H8A—C8—H8B	109.5
C5—C4—C3	119.5 (6)	O3—C8—H8C	109.5
C5—C4—C7	120.4 (6)	H8A—C8—H8C	109.5
C3—C4—C7	120.1 (5)	H8B—C8—H8C	109.5
C4—C5—C6	119.3 (6)	C2—O1—H1	109.5
C4—C5—H5	120.3	C7—O3—C8	116.9 (6)
C6—C5—H5	120.3

C6—C1—C2—O1	178.1 (6)	C2—C1—C6—C5	1.7 (11)
Br1—C1—C2—O1	−1.8 (8)	Br1—C1—C6—C5	−178.5 (5)
C6—C1—C2—C3	−0.9 (10)	C4—C5—C6—C1	−0.3 (10)
Br1—C1—C2—C3	179.2 (5)	C5—C4—C7—O2	171.3 (7)
O1—C2—C3—C4	179.8 (6)	C3—C4—C7—O2	−7.8 (10)
C1—C2—C3—C4	−1.2 (9)	C5—C4—C7—O3	−10.2 (9)
C2—C3—C4—C5	2.6 (10)	C3—C4—C7—O3	170.7 (6)
C2—C3—C4—C7	−178.3 (6)	O2—C7—O3—C8	−7.1 (10)
C3—C4—C5—C6	−1.8 (10)	C4—C7—O3—C8	174.4 (5)
C7—C4—C5—C6	179.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.87	2.681 (7)	170

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₇BrO₃
M_r	231.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.812 (4), 6.317 (2), 12.490 (5)
β (°)	100.164 (6)
V (Å³)	839.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.86
Crystal size (mm)	0.27 × 0.24 × 0.16

Data collection
Diffractometer	Bruker SMART CCD 1000
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.354, 0.511
No. of measured, independent and observed [I > 2σ(I)] reflections	4755, 1831, 1129
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.172, 1.08
No. of reflections	1831
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.55

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SAINT-Plus (Bruker, 1999, 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
O1—H1···O2ⁱ	0.82	1.87	2.681 (7)	170

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Acknowledgements

This work was funded by the 211 project of Guangdong Province.

References

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