5 Bromo­salicylic acid

organic papers

o1310

Structure Reports

Online

ISSN 1600-5368

5-Bromosalicylic acid

Zhao-Di Liu,a_{Yang Qu,}b Min-Yu Tanb_and Hai-Liang Zhua_*

a_{Department of Chemistry, Fuyang Normal}

College, Fuyang, Anhui 236041, People's Republic of China, andb_{Department of} Chemistry, Lanzhou University, Lanzhou 730000, People's Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.008 AÊ

Rfactor = 0.048

wRfactor = 0.111

Data-to-parameter ratio = 14.5

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C7H5BrO3, crystallizes with two

inde-pendent molecules in the asymmetric unit. All the O atoms in the two molecules contribute to the formation of a three-dimensional hydrogen-bonded network.

Comment

The asymmetric unit of the title complex, (I), consists of two independent molecules of 5-bromosalicylic acid (Fig. 1). In both independent molecules, the bond lengths and angles are in the normal ranges. The CÐC bond lengths of the benzene rings are in the range 1.353 (7)±1.404 (7) AÊ, the C5ÐBr1 bond length is 1.904 (5) AÊ and the Br2ÐC12 bond length is 1.897 (5) AÊ. The C1ÐC6 and C8ÐC13 rings are planar, with a mean deviation of 0.0033 AÊ. The benzene rings of the two independent molecules in the asymmetric unit are almost perpendicular to one another, with a dihedral angle of 89.1 (3)_.

All the O atoms in the two independent molecules contribute to the formation of intermolecular hydrogen bonds, so forming a three-dimensional network (details are given in Table 1 and Fig. 2).

Experimental

Crystals of compound (I) were obtained by evaporation of an ethanol±water (1:2 v/v, 10 ml) solution of 5-bromosalicylic acid (1 mmol, 0.22 g). Colorless crystals of (I) were collected, washed with water and dried in a vacuum using CaCl2(yield 42.5%). Elemental

analysis found: C 38.68, H 2.40, Br 36.77%; calculated for C7H5BrO3:

C 38.74, H 2.32, Br 36.82%.

Received 5 July 2004 Accepted 6 July 2004 Online 9 July 2004

Figure 1

Crystal data

C7H5BrO3

Mr= 217.02

Triclinic,P1

a= 4.8050 (10) AÊ

b= 12.047 (2) AÊ

c= 14.666 (3) AÊ

= 114.06 (3)

= 90.40 (3)

= 101.19 (3)

V= 756.9 (3) AÊ3

Z= 4

Dx= 1.904 Mg mÿ3

MoKradiation Cell parameters from 2884

re¯ections

= 6±27.5

= 5.38 mmÿ1

T= 293 (2) K Rod, colorless 0.140.060.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer

'and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.514,Tmax= 0.767 5095 measured re¯ections

2884 independent re¯ections 1786 re¯ections withI> 2(I)

Rint= 0.036

max= 26.0

h=ÿ5!5

k=ÿ14!14

l=ÿ18!18

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.048}

wR(F2_{) = 0.111}

S= 0.95 2884 re¯ections 199 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0474P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.003

max= 0.52 e AÊÿ3

min=ÿ0.29 e AÊÿ3

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O1ÐH1A O2i _{0.85 1.83 2.681 (5) 179} O3ÐH3B O2 0.85 1.87 2.614 (5) 145 O4ÐH4B O5ii _{0.85 1.80 2.648 (5) 177} O6ÐH6C O5 0.85 1.90 2.633 (5) 144

Symmetry codes: (i) 2ÿx;ÿy;2ÿz; (ii)ÿx;1ÿy;1ÿz.

All the H atoms were placed in geometrically idealized positions (CÐH = 0.96 AÊ and OÐH = 0.85 AÊ) and allowed to ride on their parent atoms withUiso(H) = 0.08 AÊ2.

Data collection:SMART(Siemens, 1996); cell re®nement:SAINT; data reduction: SAINT(Siemens, 1996); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.

The authors thank the Education Of®ce of Anhui Province, People's Republic of China, for research grant No. 2004kj300zd.

References

Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Sheldrick, G. M. (1997b).SHELXTL.Version. 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Figure 2

supporting information

sup-1 Acta Cryst. (2004). E60, o1310–o1311

supporting information

Acta Cryst. (2004). E60, o1310–o1311 [https://doi.org/10.1107/S1600536804016411]

5-Bromosalicylic acid

Zhao-Di Liu, Yang Qu, Min-Yu Tan and Hai-Liang Zhu

(I)

Crystal data

C7H5BrO3 Mr = 217.02

Triclinic, P1 Hall symbol: -P 1 a = 4.805 (1) Å b = 12.047 (2) Å c = 14.666 (3) Å α = 114.06 (3)° β = 90.40 (3)° γ = 101.19 (3)° V = 756.9 (3) Å3

Z = 4 F(000) = 424 Dx = 1.904 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2884 reflections θ = 6–27.5°

µ = 5.38 mm−1 T = 293 K Needle, colorless 0.14 × 0.06 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.514, Tmax = 0.767

5095 measured reflections 2884 independent reflections 1786 reflections with I > 2σ(I) Rint = 0.036

θmax = 26.0°, θmin = 1.5° h = −5→5

k = −14→14 l = −18→18

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.048} wR(F2_{) = 0.111} S = 0.95 2884 reflections 199 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0474P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.003

Δρmax = 0.52 e Å−3 Δρmin = −0.29 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Br1 0.25119 (15) 0.48915 (6) 1.17770 (5) 0.0856 (3) Br2 1.18701 (11) 0.81837 (5) 0.36237 (4) 0.0617 (2) C1 0.5842 (9) 0.1934 (5) 0.9862 (4) 0.0453 (12) C2 0.4840 (10) 0.1796 (5) 0.8913 (4) 0.0517 (13) C3 0.3207 (11) 0.2593 (5) 0.8842 (4) 0.0569 (14) H3A 0.2526 0.2495 0.8191 0.080* C4 0.2555 (12) 0.3509 (5) 0.9682 (5) 0.0631 (15) H4A 0.1427 0.4059 0.9627 0.080* C5 0.3520 (11) 0.3630 (5) 1.0618 (4) 0.0539 (13) C6 0.5135 (10) 0.2875 (5) 1.0717 (4) 0.0520 (13) H6A 0.5801 0.2982 1.1372 0.080* C7 0.7631 (10) 0.1111 (5) 0.9956 (4) 0.0527 (13) C8 0.6147 (9) 0.7144 (4) 0.5390 (4) 0.0425 (12) C9 0.7277 (11) 0.7988 (5) 0.6366 (4) 0.0478 (12) C10 0.9752 (11) 0.8867 (5) 0.6504 (4) 0.0543 (14) H10A 1.0527 0.9449 0.7171 0.080* C11 1.1106 (11) 0.8911 (5) 0.5699 (4) 0.0523 (13) H11A 1.2839 0.9517 0.5800 0.080* C12 0.9997 (10) 0.8090 (5) 0.4732 (4) 0.0458 (12) C13 0.7562 (10) 0.7204 (4) 0.4573 (4) 0.0429 (12) H13A 0.6814 0.6627 0.3901 0.080* C14 0.3498 (10) 0.6208 (4) 0.5223 (4) 0.0415 (11) O1 0.8472 (8) 0.1329 (3) 1.0875 (3) 0.0646 (10) H1A 0.9495 0.0820 1.0857 0.080* O2 0.8317 (8) 0.0295 (4) 0.9219 (3) 0.0626 (10) O3 0.5389 (8) 0.0905 (4) 0.8053 (3) 0.0647 (10) H3B 0.6431 0.0485 0.8187 0.080* O4 0.2719 (7) 0.5438 (3) 0.4282 (2) 0.0548 (9) H4B 0.1153 0.4942 0.4244 0.080* O5 0.2157 (7) 0.6147 (3) 0.5919 (3) 0.0535 (9) O6 0.6054 (8) 0.8009 (3) 0.7193 (3) 0.0674 (11) H6C 0.4536 0.7446 0.7026 0.080*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2004). E60, o1310–o1311

C3 0.059 (3) 0.057 (4) 0.054 (4) 0.006 (3) −0.006 (3) 0.026 (3) C4 0.065 (4) 0.058 (4) 0.072 (4) 0.011 (3) 0.002 (3) 0.035 (3) C5 0.052 (3) 0.050 (3) 0.059 (4) 0.005 (3) 0.005 (3) 0.025 (3) C6 0.052 (3) 0.058 (4) 0.049 (3) 0.003 (3) 0.002 (3) 0.029 (3) C7 0.039 (3) 0.060 (4) 0.056 (4) −0.007 (3) −0.001 (3) 0.029 (3) C8 0.038 (3) 0.038 (3) 0.052 (3) 0.012 (2) −0.001 (2) 0.017 (3) C9 0.050 (3) 0.043 (3) 0.045 (3) 0.008 (3) −0.001 (2) 0.013 (3) C10 0.050 (3) 0.048 (3) 0.051 (3) 0.002 (3) −0.003 (3) 0.010 (3) C11 0.047 (3) 0.039 (3) 0.064 (4) 0.001 (2) −0.004 (3) 0.018 (3) C12 0.043 (3) 0.047 (3) 0.052 (3) 0.012 (2) 0.003 (2) 0.023 (3) C13 0.044 (3) 0.037 (3) 0.043 (3) 0.011 (2) −0.002 (2) 0.011 (2) C14 0.042 (3) 0.038 (3) 0.043 (3) 0.011 (2) 0.004 (2) 0.015 (3) O1 0.074 (3) 0.075 (3) 0.055 (2) 0.026 (2) 0.0056 (19) 0.033 (2) O2 0.067 (2) 0.062 (3) 0.053 (2) 0.015 (2) −0.0026 (19) 0.019 (2) O3 0.069 (2) 0.070 (3) 0.048 (2) 0.021 (2) −0.0042 (18) 0.015 (2) O4 0.049 (2) 0.053 (2) 0.048 (2) −0.0019 (17) 0.0023 (16) 0.0119 (19) O5 0.054 (2) 0.051 (2) 0.047 (2) 0.0015 (17) 0.0045 (17) 0.0165 (18) O6 0.063 (2) 0.073 (3) 0.047 (2) −0.005 (2) 0.0054 (18) 0.013 (2)

Geometric parameters (Å, º)

Br1—C5 1.904 (5) C8—C13 1.403 (6) Br2—C12 1.897 (5) C8—C14 1.471 (6) C1—C6 1.403 (7) C9—O6 1.345 (6) C1—C2 1.404 (7) C9—C10 1.381 (7) C1—C7 1.476 (7) C10—C11 1.367 (7) C2—O3 1.350 (6) C10—H10A 0.9600 C2—C3 1.386 (7) C11—C12 1.384 (7) C3—C4 1.366 (7) C11—H11A 0.9600 C3—H3A 0.9601 C12—C13 1.368 (7) C4—C5 1.387 (7) C13—H13A 0.9600 C4—H4A 0.9602 C14—O5 1.231 (5) C5—C6 1.353 (7) C14—O4 1.312 (5) C6—H6A 0.9601 O1—H1A 0.8499 C7—O2 1.227 (6) O3—H3B 0.8500 C7—O1 1.309 (6) O4—H4B 0.8500 C8—C9 1.402 (6) O6—H6C 0.8500

C3—C4—H4A 120.5 C13—C12—C11 120.3 (5) C5—C4—H4A 120.2 C13—C12—Br2 119.8 (4) C6—C5—C4 121.4 (5) C11—C12—Br2 119.9 (4) C6—C5—Br1 120.2 (4) C12—C13—C8 119.9 (4) C4—C5—Br1 118.4 (4) C12—C13—H13A 120.0 C5—C6—C1 120.1 (5) C8—C13—H13A 120.0 C5—C6—H6A 120.0 O5—C14—O4 123.0 (4) C1—C6—H6A 119.8 O5—C14—C8 122.2 (5) O2—C7—O1 122.6 (5) O4—C14—C8 114.8 (4) O2—C7—C1 122.0 (5) C7—O1—H1A 108.8 O1—C7—C1 115.3 (5) C2—O3—H3B 109.7 C9—C8—C13 119.3 (5) C14—O4—H4B 109.4 C9—C8—C14 120.4 (5) C9—O6—H6C 109.6

C6—C1—C2—O3 −179.1 (4) C13—C8—C9—O6 179.3 (4) C7—C1—C2—O3 1.6 (7) C14—C8—C9—O6 −0.4 (7) C6—C1—C2—C3 0.5 (7) C13—C8—C9—C10 0.3 (7) C7—C1—C2—C3 −178.8 (4) C14—C8—C9—C10 −179.4 (4) O3—C2—C3—C4 179.5 (5) O6—C9—C10—C11 −179.4 (5) C1—C2—C3—C4 −0.1 (8) C8—C9—C10—C11 −0.4 (8) C2—C3—C4—C5 −0.7 (8) C9—C10—C11—C12 1.0 (8) C3—C4—C5—C6 1.2 (8) C10—C11—C12—C13 −1.5 (8) C3—C4—C5—Br1 −178.7 (4) C10—C11—C12—Br2 178.9 (4) C4—C5—C6—C1 −0.8 (8) C11—C12—C13—C8 1.4 (7) Br1—C5—C6—C1 179.1 (3) Br2—C12—C13—C8 −179.0 (3) C2—C1—C6—C5 −0.1 (7) C9—C8—C13—C12 −0.8 (7) C7—C1—C6—C5 179.3 (4) C14—C8—C13—C12 178.9 (4) C6—C1—C7—O2 −178.8 (5) C9—C8—C14—O5 1.6 (7) C2—C1—C7—O2 0.5 (7) C13—C8—C14—O5 −178.1 (4) C6—C1—C7—O1 0.0 (7) C9—C8—C14—O4 −177.2 (4) C2—C1—C7—O1 179.3 (4) C13—C8—C14—O4 3.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1A···O2i _{0.85 1.83 2.681 (5) 179} O3—H3B···O2 0.85 1.87 2.614 (5) 145 O4—H4B···O5ii _{0.85 1.80 2.648 (5) 177} O6—H6C···O5 0.85 1.90 2.633 (5) 144