6-Bromo-1H-indole-3-carb­oxy­lic acid

Zhao, J.; Wang, Y.

doi:10.1107/S1600536812006381

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1019

doi:10.1107/S1600536812006381

Open

access

6-Bromo-1H-indole-3-carboxylic acid

Jing Zhao ^a ^* and Yan Wang ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 3 December 2011; accepted 13 February 2012; online 10 March 2012)

In the title molecule, C₉H₆BrNO₂, the dihedral angle between the –COOH group and the ring system is 6 (4)°. In the crystal, pairs of O—H⋯O hydrogen bonds link the molecules into inversion dimers and these dimers are connected via N—H⋯O hydrogen bonds to form layers parallel to the (-101) plane.

Related literature

For related literature, see: Lang et al. (2011 ); Luo et al. (2011 ).

Experimental

Crystal data

C₉H₆BrNO₂
M_r = 240.06
Monoclinic, P 2₁ /n
a = 7.2229 (14) Å
b = 11.874 (2) Å
c = 11.079 (2) Å
β = 108.37 (3)°
V = 901.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.52 mm⁻¹
T = 293 K
0.30 × 0.23 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.977, T_max = 0.984
8876 measured reflections
2051 independent reflections
1284 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.158
S = 1.06
2051 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H7⋯O1ⁱ	0.97 (9)	1.67 (10)	2.627 (5)	169 (8)
N1—H1A⋯O1ⁱⁱ	0.86	2.16	2.928 (6)	148
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812006381/aa2041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006381/aa2041Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006381/aa2041Isup3.cml

checkCIF report

Comment top

Indole derivatives such as indole-3-carboxylates are important building blocks in the synthesis of many pharmaceuticals and biologically active compounds. (Lang et al., 2011; Luo, et al., 2011). In the crystal structure of the title compound (Fig. 1), intermolecular O—H···O hydrogen bonds link the molecules into dimers and the dimers are connected via intermolecular N—H···O hydrogen bonds forming layers parallel to (101) plane (Table 1, Fig. 2).

Related literature top

For related literature, see: Lang et al. (2011); Luo et al. (2011).

Experimental top

A solution of the title compound (0.2 g) in methanol (20 ml) was placed in a dark place. Yellow single crystals suitable for X-ray diffraction study were obtained by slow evaporation of the solution over a period of 7 d.

Structure description top

For related literature, see: Lang et al. (2011); Luo et al. (2011).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom labelling scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A packing diagram of the title compound. Intermolecular hydrogen bonds are shown as dashed lines.

6-Bromo-1H-indole-3-carboxylic acid top

Crystal data top

C₉H₆BrNO₂	F(000) = 472
M_r = 240.06	D_x = 1.768 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2051 reflections
a = 7.2229 (14) Å	θ = 3.0–27.5°
b = 11.874 (2) Å	µ = 4.52 mm⁻¹
c = 11.079 (2) Å	T = 293 K
β = 108.37 (3)°	Prism, brown
V = 901.7 (3) Å³	0.30 × 0.23 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2051 independent reflections
Radiation source: fine-focus sealed tube	1284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→14
T_min = 0.977, T_max = 0.984	l = −14→14
8876 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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0513P)² + 1.7606P] where P = (F_o² + 2F_c²)/3
2051 reflections	(Δ/σ)_max < 0.001
122 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₉H₆BrNO₂	V = 901.7 (3) Å³
M_r = 240.06	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2229 (14) Å	µ = 4.52 mm⁻¹
b = 11.874 (2) Å	T = 293 K
c = 11.079 (2) Å	0.30 × 0.23 × 0.20 mm
β = 108.37 (3)°

Data collection top

Rigaku SCXmini diffractometer	2051 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1284 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.984	R_int = 0.082
8876 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.52 e Å⁻³
2051 reflections	Δρ_min = −0.76 e Å⁻³
122 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	0.08018 (10)	0.38905 (7)	0.15536 (6)	0.0777 (4)
C5	0.2174 (7)	0.5896 (4)	0.4756 (5)	0.0394 (12)
O2	0.4390 (7)	0.4389 (3)	0.8444 (4)	0.0571 (12)
O1	0.4564 (6)	0.6167 (3)	0.9140 (3)	0.0453 (9)
C3	0.4157 (7)	0.5477 (4)	0.8231 (5)	0.0369 (12)
N1	0.2185 (7)	0.6961 (4)	0.5252 (4)	0.0457 (11)
H1A	0.1800	0.7563	0.4813	0.055*
C4	0.2939 (7)	0.5144 (4)	0.5765 (5)	0.0366 (11)
C9	0.3036 (8)	0.4004 (5)	0.5495 (5)	0.0452 (13)
H9A	0.3525	0.3484	0.6146	0.054*
C8	0.2397 (9)	0.3663 (5)	0.4251 (6)	0.0504 (14)
H8A	0.2447	0.2902	0.4063	0.060*
C2	0.3405 (7)	0.5824 (4)	0.6922 (5)	0.0361 (11)
C1	0.2896 (7)	0.6912 (4)	0.6539 (5)	0.0421 (13)
H1B	0.3021	0.7525	0.7082	0.051*
C7	0.1676 (7)	0.4426 (5)	0.3265 (5)	0.0440 (13)
C6	0.1550 (7)	0.5551 (5)	0.3481 (5)	0.0459 (14)
H6A	0.1075	0.6061	0.2818	0.055*
H7	0.484 (13)	0.427 (7)	0.936 (9)	0.13 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0665 (5)	0.1168 (7)	0.0510 (4)	−0.0166 (4)	0.0201 (3)	−0.0338 (4)
C5	0.037 (3)	0.040 (3)	0.041 (3)	0.000 (2)	0.012 (2)	−0.002 (2)
O2	0.095 (3)	0.029 (2)	0.041 (2)	−0.002 (2)	0.012 (2)	0.0027 (17)
O1	0.065 (2)	0.0304 (19)	0.038 (2)	−0.0045 (18)	0.0119 (18)	−0.0017 (15)
C3	0.039 (3)	0.032 (3)	0.039 (3)	0.000 (2)	0.011 (2)	−0.001 (2)
N1	0.057 (3)	0.035 (2)	0.043 (3)	0.009 (2)	0.014 (2)	0.011 (2)
C4	0.038 (3)	0.035 (3)	0.037 (3)	−0.001 (2)	0.013 (2)	−0.001 (2)
C9	0.055 (3)	0.041 (3)	0.042 (3)	0.003 (3)	0.018 (3)	0.003 (2)
C8	0.058 (4)	0.044 (3)	0.055 (4)	−0.008 (3)	0.026 (3)	−0.015 (3)
C2	0.039 (3)	0.032 (3)	0.037 (3)	−0.004 (2)	0.012 (2)	−0.001 (2)
C1	0.047 (3)	0.032 (3)	0.044 (3)	0.001 (2)	0.011 (3)	−0.002 (2)
C7	0.039 (3)	0.060 (4)	0.036 (3)	−0.009 (3)	0.016 (2)	−0.010 (3)
C6	0.040 (3)	0.064 (4)	0.031 (3)	0.003 (3)	0.008 (2)	0.006 (3)

Geometric parameters (Å, º) top

Br1—C7	1.908 (5)	C4—C9	1.394 (7)
C5—N1	1.377 (7)	C4—C2	1.461 (7)
C5—C6	1.402 (7)	C9—C8	1.369 (8)
C5—C4	1.401 (7)	C9—H9A	0.9300
O2—C3	1.315 (6)	C8—C7	1.388 (8)
O2—H7	0.97 (9)	C8—H8A	0.9300
O1—C3	1.259 (6)	C2—C1	1.374 (7)
C3—C2	1.439 (7)	C1—H1B	0.9300
N1—C1	1.356 (6)	C7—C6	1.365 (8)
N1—H1A	0.8600	C6—H6A	0.9300

N1—C5—C6	129.0 (5)	C9—C8—C7	121.5 (5)
N1—C5—C4	108.4 (4)	C9—C8—H8A	119.2
C6—C5—C4	122.6 (5)	C7—C8—H8A	119.2
C3—O2—H7	108 (5)	C1—C2—C3	124.0 (5)
O1—C3—O2	120.8 (5)	C1—C2—C4	106.5 (4)
O1—C3—C2	122.6 (4)	C3—C2—C4	129.4 (5)
O2—C3—C2	116.6 (5)	N1—C1—C2	109.9 (5)
C1—N1—C5	109.5 (4)	N1—C1—H1B	125.0
C1—N1—H1A	125.3	C2—C1—H1B	125.0
C5—N1—H1A	125.3	C6—C7—C8	122.0 (5)
C9—C4—C5	118.8 (5)	C6—C7—Br1	118.7 (4)
C9—C4—C2	135.4 (5)	C8—C7—Br1	119.3 (4)
C5—C4—C2	105.8 (4)	C7—C6—C5	116.4 (5)
C8—C9—C4	118.7 (5)	C7—C6—H6A	121.8
C8—C9—H9A	120.7	C5—C6—H6A	121.8
C4—C9—H9A	120.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H7···O1ⁱ	0.97 (9)	1.67 (10)	2.627 (5)	169 (8)
N1—H1A···O1ⁱⁱ	0.86	2.16	2.928 (6)	148

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

Experimental details

Crystal data
Chemical formula	C₉H₆BrNO₂
M_r	240.06
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.2229 (14), 11.874 (2), 11.079 (2)
β (°)	108.37 (3)
V (Å³)	901.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.52
Crystal size (mm)	0.30 × 0.23 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.977, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	8876, 2051, 1284
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.158, 1.06
No. of reflections	2051
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.76

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H7···O1ⁱ	0.97 (9)	1.67 (10)	2.627 (5)	169 (8)
N1—H1A···O1ⁱⁱ	0.86	2.16	2.928 (6)	148.0

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

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Lang, L., Wu, J.-L., Shi, L.-J., Xia, C.-G. & Li, F.-W. (2011). Chem. Commun. 47, 12553–12555. Web of Science CSD CrossRef CAS Google Scholar
Luo, Y.-H., Qian, X.-M., Gao, G., Li, J.-F. & Mao, S.-L. (2011). Acta Cryst. E67, m172. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1019

doi:10.1107/S1600536812006381

Open

access