2-Bromo­pyridine-3-carboxylic acid

Howie, R.A.; Gonçalves, R.S.; Souza, M.V.N. de; Tiekink, E.R.T.; Wardell, J.L.

doi:10.1107/S1600536810003314

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o486

https://doi.org/10.1107/S1600536810003314

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2-Bromopyridine-3-carboxylic acid

R. Alan Howie,^a Raoni S. Gonçalves,^b Marcus V. N. de Souza,^b Edward R. T. Tiekink ^c ^* and James L. Wardell ^d ‡

^aDepartment of Chemistry, University of Aberdeen, Old Aberdeen AB15 5NY, Scotland, ^bInstituto de Tecnologia em Farmacos, Fundação Oswaldo Cruz (FIOCRUZ), Far-Manguinhos, Rua Sizenando Nabuco, 100, Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dCentro de Desenvolvimento Tecnológico em Saúde (CDTS), Fundação Oswaldo Cruz (FIOCRUZ), Casa Amarela, Campus de Manguinhos, Av. Brasil 4365, 21040-900 Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 26 January 2010; accepted 27 January 2010; online 30 January 2010)

The carboxylic acid residue in the title compound, C₆H₄BrNO₂, is twisted out of the plane of the other atoms, as indicated by the (Br)C—C—C—O_carbonyl torsion angle of −20.1 (9)°. In the crystal, supramolecular chains mediated by O—H⋯N hydrogen bonds are formed with base vector [201] and C—H⋯O interactions reinforce the packing.

Related literature

For the biological activity of N-heterocylic compounds, see: de Souza (2005 ); Cunico et al. (2006 ). For related structures, see: Wright & King (1953 ); Kutoglu & Scheringer (1983 ); de Souza et al. (2005 ); Kaiser et al. (2009 ). For the synthesis, see: Bradlow & van der Werf (1949 ).

Experimental

Crystal data

C₆H₄BrNO₂
M_r = 202.01
Monoclinic, P 2₁ /c
a = 3.9286 (3) Å
b = 12.9737 (9) Å
c = 12.8570 (8) Å
β = 96.695 (4)°
V = 650.83 (8) Å³
Z = 4
Mo Kα radiation
μ = 6.24 mm⁻¹
T = 120 K
0.10 × 0.09 × 0.08 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.453, T_max = 0.607
7699 measured reflections
1147 independent reflections
882 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.093
S = 1.06
1147 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.84	1.85	2.685 (5)	173
C5—H5⋯O2ⁱⁱ	0.95	2.39	3.258 (7)	152
C6—H6⋯O2ⁱⁱⁱ	0.95	2.47	3.171 (6)	131
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; 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 DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810003314/hb5318sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810003314/hb5318Isup2.hkl

checkCIF report

Comment top

The structure of the title compound, (I), was determined in connection with on-going studies of biological activitiess, e.g. anti-mycobacterial activity, of N-heterocyclic compounds (Cunico et al. 2006; de Souza, 2005), as we have embarked on complementary systematic structural investigations in order to ascertain supramolecular aggregation patterns (Kaiser et al., 2009).

In the molecular structure of (I), Fig. 1, the carbonyl-O2 atom is approximately syn to the bromide. The carboxylic acid residue is twisted out of the plane of the pyridine ring as seen in the value of the C2/C3/C7/O1 torsion angle of 161.1 (5)°. In the crystal packing, a supramolecular chain with base vector [2 0 1] is formed through the agency of O–H···N hydrogen bonds, Fig. 2 and Table 1. Additional stabilisation to the chains are afforded by C–H···O_carbonyl interactions, Table 1. The chains stack into layers in the ab place and are consolidated in the crystal structure by further C–H···O_carbonyl contacts, Fig. 2 & Table 1. Similar supramolecular chains are found in the crystal structures of nicotinic acid (Wright & King, 1953; Kutoglu & Scheringer, 1983) as well as in 2-chloropyridine-3-carboxylic acid (de Souza et al., 2005).

Related literature top

For the biological activity of N-heterocylic compounds, see: de Souza (2005); Cunico et al. (2006). For related structures, see: Wright & King (1953); Kutoglu & Scheringer (1983); de Souza et al. (2005); Kaiser et al. (2009). For the synthesis, see: Bradlow & van der Werf (1949).

Experimental top

A mixture of 2-bromo-3-methylpyridine (0.77 g, 4.5 mmol), KMnO₄ (0.316 g, 2 mmol) and H₂O (20 ml) was refluxed until the purple colour of the solution disappeared. A second portion of KMnO₄ (0.316 g) and water (10 ml) were added and the reaction mixture was refluxed again until no purple colour remained. The reaction mixture was concentrated to 10 ml, acidified with concentrated hydrochloric acid, and filtered. The precipitate was washed with cold water and cold diethylether (20 ml). The yield was 0.79 g (60%), m.p. 520–523 K; lit value 522-523 K (Bradlow & van der Werf, 1949). 2-Bromonicotinic acid was recrystallised from EtOH for the crystallographic study. ¹H NMR [500.00 MHz, DMSO-d₆] δ: 8.50 (1H, dd, J = 5.0 and 2.0 Hz, H6), 8.13 (1H, dd, J = 7.5 and 2.0 Hz, H4), 7.55 (1H, dd, J = 7.5 and 5.0 Hz, H5), 3.44 (1H, s, OH) p.p.m. ¹³C NMR (125.0 MHz, DMSO-d₆) δ: 166.3, 151.8, 139.1, 138.6, 131.1, 123.2 p.p.m.

Structure description top

For the biological activity of N-heterocylic compounds, see: de Souza (2005); Cunico et al. (2006). For related structures, see: Wright & King (1953); Kutoglu & Scheringer (1983); de Souza et al. (2005); Kaiser et al. (2009). For the synthesis, see: Bradlow & van der Werf (1949).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); 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 DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. View of the unit cell contents in (I) highlighting the N–H···O hydrogen bonding (orange dashed lines) leading to supramolecular chains, and C–H···O contacts within and between chains (blue dashed lines). Colour code: Br, olive; O, red; N, blue; C, grey; and H, green.

2-Bromopyridine-3-carboxylic acid top

Crystal data top

C₆H₄BrNO₂	F(000) = 392
M_r = 202.01	D_x = 2.062 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 24006 reflections
a = 3.9286 (3) Å	θ = 2.9–27.5°
b = 12.9737 (9) Å	µ = 6.24 mm⁻¹
c = 12.8570 (8) Å	T = 120 K
β = 96.695 (4)°	Block, colourless
V = 650.83 (8) Å³	0.10 × 0.09 × 0.08 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	1147 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	882 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.070
Detector resolution: 9.091 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
φ and ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −15→15
T_min = 0.453, T_max = 0.607	l = −15→13
7699 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0439P)² + 1.1585P] where P = (F_o² + 2F_c²)/3
1147 reflections	(Δ/σ)_max = 0.001
92 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

C₆H₄BrNO₂	V = 650.83 (8) Å³
M_r = 202.01	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9286 (3) Å	µ = 6.24 mm⁻¹
b = 12.9737 (9) Å	T = 120 K
c = 12.8570 (8) Å	0.10 × 0.09 × 0.08 mm
β = 96.695 (4)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1147 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	882 reflections with I > 2σ(I)
T_min = 0.453, T_max = 0.607	R_int = 0.070
7699 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.06	Δρ_max = 0.86 e Å⁻³
1147 reflections	Δρ_min = −0.62 e Å⁻³
92 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br	0.26644 (13)	0.59770 (4)	0.89357 (4)	0.0284 (2)
O1	−0.1485 (10)	0.8088 (3)	0.6204 (3)	0.0329 (9)
H1	−0.2563	0.7783	0.5691	0.049*
O2	0.0225 (11)	0.6488 (3)	0.6647 (3)	0.0484 (12)
N1	0.5499 (10)	0.7843 (3)	0.9471 (3)	0.0257 (10)
C2	0.3563 (13)	0.7384 (4)	0.8676 (4)	0.0237 (11)
C3	0.2287 (12)	0.7899 (4)	0.7756 (4)	0.0246 (11)
C4	0.3069 (14)	0.8942 (4)	0.7698 (4)	0.0303 (12)
H4	0.2193	0.9327	0.7098	0.036*
C5	0.5111 (13)	0.9428 (4)	0.8507 (4)	0.0252 (12)
H5	0.5688	1.0137	0.8461	0.030*
C6	0.6276 (13)	0.8854 (4)	0.9378 (4)	0.0268 (12)
H6	0.7679	0.9179	0.9935	0.032*
C7	0.0240 (13)	0.7406 (4)	0.6822 (4)	0.0290 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0342 (3)	0.0217 (3)	0.0277 (3)	−0.0033 (2)	−0.0029 (2)	0.0016 (2)
O1	0.042 (2)	0.030 (2)	0.025 (2)	0.0023 (18)	−0.0059 (17)	−0.0007 (16)
O2	0.072 (3)	0.027 (2)	0.041 (2)	0.009 (2)	−0.018 (2)	−0.0066 (19)
N1	0.031 (2)	0.024 (2)	0.023 (2)	0.0023 (19)	0.0034 (19)	−0.0008 (19)
C2	0.021 (2)	0.024 (3)	0.026 (3)	0.002 (2)	0.005 (2)	−0.001 (2)
C3	0.023 (3)	0.026 (3)	0.024 (3)	0.005 (2)	0.002 (2)	−0.003 (2)
C4	0.035 (3)	0.025 (3)	0.029 (3)	0.003 (2)	−0.003 (2)	0.003 (2)
C5	0.030 (3)	0.020 (3)	0.026 (3)	−0.001 (2)	0.003 (2)	−0.003 (2)
C6	0.027 (3)	0.028 (3)	0.024 (3)	0.000 (2)	−0.002 (2)	−0.007 (2)
C7	0.028 (3)	0.031 (3)	0.027 (3)	0.003 (2)	0.000 (2)	0.002 (2)

Geometric parameters (Å, º) top

Br—C2	1.897 (5)	C3—C4	1.392 (7)
O1—C7	1.322 (6)	C3—C7	1.507 (7)
O1—H1	0.8400	C4—C5	1.388 (7)
O2—C7	1.213 (6)	C4—H4	0.9500
N1—C2	1.340 (6)	C5—C6	1.378 (7)
N1—C6	1.356 (6)	C5—H5	0.9500
C2—C3	1.400 (7)	C6—H6	0.9500

C7—O1—H1	109.5	C3—C4—H4	119.5
C2—N1—C6	118.4 (4)	C6—C5—C4	118.1 (5)
N1—C2—C3	123.3 (5)	C6—C5—H5	121.0
N1—C2—Br	113.2 (3)	C4—C5—H5	121.0
C3—C2—Br	123.5 (4)	N1—C6—C5	122.6 (4)
C4—C3—C2	116.7 (5)	N1—C6—H6	118.7
C4—C3—C7	118.1 (4)	C5—C6—H6	118.7
C2—C3—C7	125.2 (4)	O2—C7—O1	123.7 (5)
C5—C4—C3	120.9 (5)	O2—C7—C3	123.8 (5)
C5—C4—H4	119.5	O1—C7—C3	112.6 (4)

C2—C3—C7—O1	161.1 (5)	C2—C3—C7—O2	−20.1 (9)
C4—C3—C7—O1	−20.7 (7)	C4—C3—C7—O2	158.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84	1.85	2.685 (5)	173
C5—H5···O2ⁱⁱ	0.95	2.39	3.258 (7)	152
C6—H6···O2ⁱⁱⁱ	0.95	2.47	3.171 (6)	131

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

Experimental details

Crystal data
Chemical formula	C₆H₄BrNO₂
M_r	202.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	3.9286 (3), 12.9737 (9), 12.8570 (8)
β (°)	96.695 (4)
V (Å³)	650.83 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.24
Crystal size (mm)	0.10 × 0.09 × 0.08

Data collection
Diffractometer	Nonius KappaCCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.453, 0.607
No. of measured, independent and observed [I > 2σ(I)] reflections	7699, 1147, 882
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.093, 1.06
No. of reflections	1147
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.62

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84	1.85	2.685 (5)	173
C5—H5···O2ⁱⁱ	0.95	2.39	3.258 (7)	152
C6—H6···O2ⁱⁱⁱ	0.95	2.47	3.171 (6)	131

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

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil).

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