3,5-Dibromo-2-hydroxy­benzoic acid

Liu, C.-B.; Chen, D.-D.; Wen, H.-L.

doi:10.1107/S1600536807062320

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o3

https://doi.org/10.1107/S1600536807062320

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3,5-Dibromo-2-hydroxybenzoic acid

Chong-Bo Liu,^a Dan-Dan Chen ^b and Hui-Liang Wen ^c ^*

^aCollege of Environmental and Chemical Engineering, Nanchang University of Aeronautics, Nanchang 330063, People's Republic of China, ^bDepartment of Chemistry, Nanchang University, Nanchang 330047, People's Republic of China, and ^cState Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047, People's Republic of China
^*Correspondence e-mail: hlwen70@163.com

(Received 16 November 2007; accepted 22 November 2007; online 6 December 2007)

The title compound, C₇H₄Br₂O₃, has an intramolecular O—H⋯O=C hydrogen bond and aggregates to form hydrogen-bonded dimers via O—H⋯O interactions. The formation of zigzag one-dimensional molecular tapes via C—H⋯Br interactions and π–π stacking interactions (interplanar separation = 3.42 Å) completes the crystal structure.

Related literature

For related literature, see: Chiari et al. (1981 ); Jin & Xiao (2005 ).

Experimental

Crystal data

C₇H₄Br₂O₃
M_r = 295.92
Monoclinic, C 2/c
a = 10.770 (3) Å
b = 11.082 (3) Å
c = 14.879 (4) Å
β = 105.606 (3)°
V = 1710.4 (8) Å³
Z = 8
Mo Kα radiation
μ = 9.44 mm⁻¹
T = 293 (2) K
0.50 × 0.31 × 0.21 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.088, T_max = 0.243 (expected range = 0.050–0.138)
6362 measured reflections
1599 independent reflections
1286 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.061
S = 1.79
1599 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.81 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	2.684 (3)	175
O3—H3⋯O2	0.82	1.93	2.648 (3)	145
C3—H3A⋯Br1ⁱⁱ	0.93	2.89	3.810 (3)	172
Symmetry codes: (i) $[-x+{\script{5\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{5\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062320/gg2052sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062320/gg2052Isup2.hkl

checkCIF report

Comment top

The compound 2-hydroxybenzoic acid (salicylic acid) and its derivatives have been widely studied as medicines or important active pharmaceutical intermediates (Chiari et al., 1981; Jin & Xiao, 2005). Herein, we report the crystal structure of the title compound, (I).

In (I) (Fig. 1), the atoms O1, O2, O3, Br1, Br2, C1 and aromatic ring {C2,···,C7} are essentially coplanar with a mean deviation of 0.014 Å. The crystal packing is stabilized by intramolecular and intermolecular O—H···O and C—H···Br hydrogen bonds (Table 1).

Related literature top

For related literature, see: Chiari et al. (1981); Jin & Xiao (2005).

Experimental top

Crystals appropriate for data collection were obtained by recrystallization from ethanol (m.p. 500–501 K).

Structure description top

For related literature, see: Chiari et al. (1981); Jin & Xiao (2005).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top

Fig. 1. The molecular structure of the title compound depicted with 30% probability displacement ellipsoids.

3,5-Dibromo-2-hydroxybenzoic acid top

Crystal data top

C₇H₄Br₂O₃	F(000) = 1120
M_r = 295.92	D_x = 2.298 Mg m⁻³
Monoclinic, C2/c	Melting point: 500 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 10.770 (3) Å	Cell parameters from 2346 reflections
b = 11.082 (3) Å	θ = 2.7–26.3°
c = 14.879 (4) Å	µ = 9.44 mm⁻¹
β = 105.606 (3)°	T = 293 K
V = 1710.4 (8) Å³	Block, light-yellow
Z = 8	0.50 × 0.31 × 0.21 mm

Data collection top

Bruker SMART CCD diffractometer	1599 independent reflections
Radiation source: fine-focus sealed tube	1286 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.088, T_max = 0.243	k = −13→13
6362 measured reflections	l = −17→18

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.79	w = 1/[σ²(F_o²)] where P = (F_o² + 2F_c²)/3
1599 reflections	(Δ/σ)_max = 0.001
111 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.81 e Å⁻³

Crystal data top

C₇H₄Br₂O₃	V = 1710.4 (8) Å³
M_r = 295.92	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 10.770 (3) Å	µ = 9.44 mm⁻¹
b = 11.082 (3) Å	T = 293 K
c = 14.879 (4) Å	0.50 × 0.31 × 0.21 mm
β = 105.606 (3)°

Data collection top

Bruker SMART CCD diffractometer	1599 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1286 reflections with I > 2σ(I)
T_min = 0.088, T_max = 0.243	R_int = 0.032
6362 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.79	Δρ_max = 0.82 e Å⁻³
1599 reflections	Δρ_min = −0.81 e Å⁻³
111 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

	x	y	z	U_iso*/U_eq
Br1	1.06441 (4)	0.35585 (3)	0.42603 (3)	0.07017 (19)
Br2	0.68570 (4)	0.02983 (4)	0.22295 (3)	0.05891 (17)
O1	1.2480 (2)	−0.0861 (2)	0.49804 (18)	0.0543 (7)
H1	1.2875	−0.1464	0.5219	0.081*
O2	1.1105 (2)	−0.2248 (2)	0.41973 (16)	0.0545 (7)
O3	0.8866 (2)	−0.1506 (2)	0.31093 (18)	0.0560 (7)
H3	0.9422	−0.2005	0.3341	0.084*
C1	1.1390 (3)	−0.1185 (3)	0.4393 (2)	0.0422 (9)
C2	1.0523 (3)	−0.0171 (3)	0.3998 (2)	0.0376 (8)
C3	1.0907 (3)	0.1018 (3)	0.4246 (2)	0.0403 (9)
H3A	1.1712	0.1172	0.4654	0.048*
C4	1.0092 (3)	0.1959 (3)	0.3885 (2)	0.0412 (9)
C5	0.8890 (3)	0.1766 (3)	0.3280 (2)	0.0414 (9)
H5	0.8349	0.2410	0.3040	0.050*
C6	0.8509 (3)	0.0593 (3)	0.3040 (2)	0.0395 (9)
C7	0.9306 (3)	−0.0390 (3)	0.3386 (2)	0.0387 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0482 (3)	0.0329 (2)	0.1040 (4)	−0.00311 (18)	−0.0233 (2)	0.0025 (2)
Br2	0.0371 (2)	0.0526 (3)	0.0726 (3)	−0.00593 (18)	−0.0101 (2)	−0.0044 (2)
O1	0.0511 (16)	0.0353 (14)	0.0606 (17)	0.0064 (12)	−0.0126 (13)	0.0036 (12)
O2	0.0583 (17)	0.0327 (15)	0.0596 (17)	0.0041 (12)	−0.0064 (13)	−0.0017 (12)
O3	0.0514 (16)	0.0348 (15)	0.0690 (18)	−0.0019 (12)	−0.0056 (13)	−0.0074 (13)
C1	0.039 (2)	0.043 (2)	0.041 (2)	0.0019 (17)	0.0051 (17)	0.0040 (17)
C2	0.040 (2)	0.033 (2)	0.037 (2)	0.0013 (16)	0.0032 (17)	0.0044 (15)
C3	0.0332 (19)	0.037 (2)	0.043 (2)	−0.0024 (16)	−0.0032 (16)	0.0013 (16)
C4	0.041 (2)	0.0296 (19)	0.047 (2)	−0.0045 (15)	0.0024 (18)	0.0026 (16)
C5	0.0325 (19)	0.036 (2)	0.050 (2)	0.0017 (16)	0.0011 (17)	0.0028 (17)
C6	0.0326 (19)	0.041 (2)	0.041 (2)	−0.0032 (16)	0.0026 (16)	−0.0023 (16)
C7	0.042 (2)	0.035 (2)	0.037 (2)	−0.0032 (17)	0.0082 (17)	−0.0017 (16)

Geometric parameters (Å, º) top

Br1—C4	1.905 (3)	C2—C3	1.401 (4)
Br2—C6	1.890 (3)	C2—C7	1.402 (5)
O1—C1	1.311 (4)	C3—C4	1.375 (5)
O1—H1	0.8200	C3—H3A	0.9300
O2—C1	1.233 (4)	C4—C5	1.381 (5)
O3—C7	1.348 (4)	C5—C6	1.380 (4)
O3—H3	0.8200	C5—H5	0.9300
C1—C2	1.478 (5)	C6—C7	1.397 (5)

C1—O1—H1	109.5	C3—C4—Br1	118.3 (3)
C7—O3—H3	109.5	C5—C4—Br1	119.9 (3)
O2—C1—O1	122.7 (3)	C6—C5—C4	118.4 (3)
O2—C1—C2	122.9 (3)	C6—C5—H5	120.8
O1—C1—C2	114.4 (3)	C4—C5—H5	120.8
C3—C2—C7	119.5 (3)	C5—C6—C7	122.0 (3)
C3—C2—C1	120.0 (3)	C5—C6—Br2	119.4 (3)
C7—C2—C1	120.4 (3)	C7—C6—Br2	118.6 (3)
C4—C3—C2	119.9 (3)	O3—C7—C6	118.2 (3)
C4—C3—H3A	120.1	O3—C7—C2	123.2 (3)
C2—C3—H3A	120.1	C6—C7—C2	118.5 (3)
C3—C4—C5	121.7 (3)

O2—C1—C2—C3	−179.7 (3)	C4—C5—C6—C7	−0.5 (5)
O1—C1—C2—C3	1.3 (5)	C4—C5—C6—Br2	179.0 (3)
O2—C1—C2—C7	1.2 (6)	C5—C6—C7—O3	−179.3 (3)
O1—C1—C2—C7	−177.8 (3)	Br2—C6—C7—O3	1.2 (4)
C7—C2—C3—C4	−0.3 (5)	C5—C6—C7—C2	0.5 (5)
C1—C2—C3—C4	−179.3 (3)	Br2—C6—C7—C2	−179.0 (2)
C2—C3—C4—C5	0.2 (5)	C3—C2—C7—O3	179.7 (3)
C2—C3—C4—Br1	178.9 (2)	C1—C2—C7—O3	−1.2 (5)
C3—C4—C5—C6	0.2 (5)	C3—C2—C7—C6	−0.1 (5)
Br1—C4—C5—C6	−178.5 (2)	C1—C2—C7—C6	179.0 (3)

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	2.684 (3)	175
O3—H3···O2	0.82	1.93	2.648 (3)	145
C3—H3A···Br1ⁱⁱ	0.93	2.89	3.810 (3)	172

Symmetry codes: (i) −x+5/2, −y−1/2, −z+1; (ii) −x+5/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₄Br₂O₃
M_r	295.92
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	10.770 (3), 11.082 (3), 14.879 (4)
β (°)	105.606 (3)
V (Å³)	1710.4 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	9.44
Crystal size (mm)	0.50 × 0.31 × 0.21

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.088, 0.243
No. of measured, independent and observed [I > 2σ(I)] reflections	6362, 1599, 1286
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.061, 1.79
No. of reflections	1599
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.81

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

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	2.684 (3)	175
O3—H3···O2	0.82	1.93	2.648 (3)	145
C3—H3A···Br1ⁱⁱ	0.93	2.89	3.810 (3)	172

Symmetry codes: (i) −x+5/2, −y−1/2, −z+1; (ii) −x+5/2, −y+1/2, −z+1.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 20662007).

References

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Jin, L.-F. & Xiao, F.-P. (2005). Acta Cryst. E61, o1198–o1199. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar