PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o486.
Published online 2010 January 30. doi:  10.1107/S1600536810003314
PMCID: PMC2979810

2-Bromo­pyridine-3-carboxylic acid

Abstract

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—Ocarbon­yl 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 [triangle]); Cunico et al. (2006 [triangle]). For related structures, see: Wright & King (1953 [triangle]); Kutoglu & Scheringer (1983 [triangle]); de Souza et al. (2005 [triangle]); Kaiser et al. (2009 [triangle]). For the synthesis, see: Bradlow & van der Werf (1949 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o486-scheme1.jpg

Experimental

Crystal data

  • C6H4BrNO2
  • M r = 202.01
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o486-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.093
  • S = 1.06
  • 1147 reflections
  • 92 parameters
  • H-atom parameters constrained
  • Δρmax = 0.86 e Å−3
  • Δρmin = −0.62 e Å−3

Data collection: COLLECT (Hooft, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003314/hb5318Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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).

supplementary crystallographic information

Comment

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 CH···Ocarbonyl interactions, Table 1. The chains stack into layers in the ab place and are consolidated in the crystal structure by further CH···Ocarbonyl 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).

Experimental

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.

Refinement

The C-bound H atoms were geometrically placed (C–H = 0.95 Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atoms were located from a difference map and refined with Uiso(H) = 1.5Ueq(N).

Figures

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 ...

Crystal data

C6H4BrNO2F(000) = 392
Mr = 202.01Dx = 2.062 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 24006 reflections
a = 3.9286 (3) Åθ = 2.9–27.5°
b = 12.9737 (9) ŵ = 6.24 mm1
c = 12.8570 (8) ÅT = 120 K
β = 96.695 (4)°Block, colourless
V = 650.83 (8) Å30.10 × 0.09 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer1147 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode882 reflections with I > 2σ(I)
10 cm confocal mirrorsRint = 0.070
Detector resolution: 9.091 pixels mm-1θmax = 25.0°, θmin = 3.2°
[var phi] and ω scansh = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)k = −15→15
Tmin = 0.453, Tmax = 0.607l = −15→13
7699 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0439P)2 + 1.1585P] where P = (Fo2 + 2Fc2)/3
1147 reflections(Δ/σ)max = 0.001
92 parametersΔρmax = 0.86 e Å3
0 restraintsΔρmin = −0.62 e Å3

Special details

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)

xyzUiso*/Ueq
Br0.26644 (13)0.59770 (4)0.89357 (4)0.0284 (2)
O1−0.1485 (10)0.8088 (3)0.6204 (3)0.0329 (9)
H1−0.25630.77830.56910.049*
O20.0225 (11)0.6488 (3)0.6647 (3)0.0484 (12)
N10.5499 (10)0.7843 (3)0.9471 (3)0.0257 (10)
C20.3563 (13)0.7384 (4)0.8676 (4)0.0237 (11)
C30.2287 (12)0.7899 (4)0.7756 (4)0.0246 (11)
C40.3069 (14)0.8942 (4)0.7698 (4)0.0303 (12)
H40.21930.93270.70980.036*
C50.5111 (13)0.9428 (4)0.8507 (4)0.0252 (12)
H50.56881.01370.84610.030*
C60.6276 (13)0.8854 (4)0.9378 (4)0.0268 (12)
H60.76790.91790.99350.032*
C70.0240 (13)0.7406 (4)0.6822 (4)0.0290 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.0342 (3)0.0217 (3)0.0277 (3)−0.0033 (2)−0.0029 (2)0.0016 (2)
O10.042 (2)0.030 (2)0.025 (2)0.0023 (18)−0.0059 (17)−0.0007 (16)
O20.072 (3)0.027 (2)0.041 (2)0.009 (2)−0.018 (2)−0.0066 (19)
N10.031 (2)0.024 (2)0.023 (2)0.0023 (19)0.0034 (19)−0.0008 (19)
C20.021 (2)0.024 (3)0.026 (3)0.002 (2)0.005 (2)−0.001 (2)
C30.023 (3)0.026 (3)0.024 (3)0.005 (2)0.002 (2)−0.003 (2)
C40.035 (3)0.025 (3)0.029 (3)0.003 (2)−0.003 (2)0.003 (2)
C50.030 (3)0.020 (3)0.026 (3)−0.001 (2)0.003 (2)−0.003 (2)
C60.027 (3)0.028 (3)0.024 (3)0.000 (2)−0.002 (2)−0.007 (2)
C70.028 (3)0.031 (3)0.027 (3)0.003 (2)0.000 (2)0.002 (2)

Geometric parameters (Å, °)

Br—C21.897 (5)C3—C41.392 (7)
O1—C71.322 (6)C3—C71.507 (7)
O1—H10.8400C4—C51.388 (7)
O2—C71.213 (6)C4—H40.9500
N1—C21.340 (6)C5—C61.378 (7)
N1—C61.356 (6)C5—H50.9500
C2—C31.400 (7)C6—H60.9500
C7—O1—H1109.5C3—C4—H4119.5
C2—N1—C6118.4 (4)C6—C5—C4118.1 (5)
N1—C2—C3123.3 (5)C6—C5—H5121.0
N1—C2—Br113.2 (3)C4—C5—H5121.0
C3—C2—Br123.5 (4)N1—C6—C5122.6 (4)
C4—C3—C2116.7 (5)N1—C6—H6118.7
C4—C3—C7118.1 (4)C5—C6—H6118.7
C2—C3—C7125.2 (4)O2—C7—O1123.7 (5)
C5—C4—C3120.9 (5)O2—C7—C3123.8 (5)
C5—C4—H4119.5O1—C7—C3112.6 (4)
C2—C3—C7—O1161.1 (5)C2—C3—C7—O2−20.1 (9)
C4—C3—C7—O1−20.7 (7)C4—C3—C7—O2158.1 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N1i0.841.852.685 (5)173
C5—H5···O2ii0.952.393.258 (7)152
C6—H6···O2iii0.952.473.171 (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

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5318).

References

  • Bradlow, H. L. & van der Werf, C. A. (1949). J. Org. Chem.14, 509–515.
  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Cunico, W., Cechinel, C. A., Bonacorso, H. G., Martins, G. M. A. P., Zanetta, N., de Souza, M. V. N., Freitas, I. Q., Soares, R. P. P. & Krettli, A. U. (2006). Bioorg. Med. Chem. Lett.16, 649–653. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Hooft, R. W. W. (1998). COLLECT Nonius BV, Delft, The Netherlands.
  • Kaiser, C. R., Pais, K. C., de Souza, M. V. N., Wardell, J. L., Wardell, S. M. S. V. & Tiekink, E. R. T. (2009). CrystEngComm, 11, 1133–1140.
  • Kutoglu, A. & Scheringer, C. (1983). Acta Cryst. C39, 232–234.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (2007). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Souza, M. V. N. de (2005). Mini Rev. Med. Chem.5, 1009–1017. [PubMed]
  • Souza, M. V. N. de, Wardell, S. M. S. V. & Howie, R. A. (2005). Acta Cryst. E61, o1347–o1349.
  • Westrip, S. P. (2010). publCIF In preparation.
  • Wright, W. B. & King, G. S. D. (1953). Acta Cryst.6, 305–317.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography