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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3161.
Published online 2009 November 21. doi:  10.1107/S1600536809047114
PMCID: PMC2971828

6-Bromo­pyridine-2-carboxamide

Abstract

In the the title compound, C6H5BrN2O, an intra­molecular N—H(...)N hydrogen bond generates an S(5) ring. In the crystal structure, inter­molecular bifurcated N—H(...)(O,O) hydrogen bonds link the mol­ecules, leading to sheets propagating in (100).

Related literature

For medicinal background to inhibitors of the crysteine protease cathepsin K, see: Altmann & Aichholz (2007 [triangle]).

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Object name is e-65-o3161-scheme1.jpg

Experimental

Crystal data

  • C6H5BrN2O
  • M r = 201.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3161-efi1.jpg
  • a = 13.034 (3) Å
  • b = 6.4050 (13) Å
  • c = 8.5540 (17) Å
  • β = 94.85 (3)°
  • V = 711.6 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 5.70 mm−1
  • T = 293 K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.395, T max = 0.599
  • 1354 measured reflections
  • 1296 independent reflections
  • 756 reflections with I > 2σ(I)
  • R int = 0.063
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.063
  • wR(F 2) = 0.172
  • S = 1.01
  • 1296 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.57 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047114/hb5211sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047114/hb5211Isup2.hkl

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

supplementary crystallographic information

Experimental

A mixture of 30 g of 6-bromopyridine-2-carboxylic acid (0.1485 mol) in 300 ml of thionyl chloide was refluxed for twenty hours. Excess thionyl chloride was removed in vacuo. The residue was added as a slurry in dioxane or benene to 75 ml cold, stirred concentrated ammonium hydroxide. The mixture was stored overnight and the filtered to give 25 g of the title compound (yield 83.4%, m.p. 417 K). Colourless blocks of (I) were obtained by the slow evaporation of an ethyl acetate solution.

Refinement

H atoms were positioned geometrically, with C-H = 0.93–0.97Å, and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) showing 50% displacement ellipsoids.
Fig. 2.
A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C6H5BrN2OF(000) = 392
Mr = 201.03Dx = 1.877 Mg m3
Monoclinic, P21/cMelting point: 417 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.034 (3) ÅCell parameters from 25 reflections
b = 6.4050 (13) Åθ = 9–12°
c = 8.5540 (17) ŵ = 5.70 mm1
β = 94.85 (3)°T = 293 K
V = 711.6 (2) Å3Block, colourless
Z = 40.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer756 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.063
graphiteθmax = 25.3°, θmin = 1.6°
ω/2θ scansh = −15→0
Absorption correction: ψ scan (North et al., 1968)k = 0→7
Tmin = 0.395, Tmax = 0.599l = −10→10
1354 measured reflections3 standard reflections every 200 reflections
1296 independent reflections intensity decay: 1%

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)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.095P)2] where P = (Fo2 + 2Fc2)/3
1296 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = −0.57 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br0.91125 (7)0.18241 (18)0.81361 (11)0.0756 (5)
O0.5752 (4)0.0268 (9)1.2691 (6)0.0584 (15)
N10.7461 (5)0.1078 (10)0.9836 (6)0.0440 (16)
N20.5728 (6)0.2794 (11)1.0883 (8)0.061 (2)
H2A0.52650.34911.13170.073*
H2B0.59700.32601.00450.073*
C10.8216 (6)0.0086 (14)0.9207 (8)0.049 (2)
C20.8389 (7)−0.2007 (15)0.9279 (9)0.057 (2)
H2C0.8929−0.26150.87980.068*
C30.7743 (7)−0.3160 (14)1.0077 (10)0.059 (2)
H3A0.7813−0.46051.01100.071*
C40.6990 (7)−0.2223 (12)1.0837 (9)0.052 (2)
H4A0.6566−0.29991.14390.062*
C50.6875 (6)−0.0119 (11)1.0690 (7)0.0408 (18)
C60.6063 (6)0.1033 (13)1.1493 (8)0.0417 (18)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.0750 (7)0.0972 (9)0.0596 (7)−0.0039 (6)0.0341 (5)0.0056 (6)
O0.084 (4)0.056 (3)0.039 (3)−0.012 (3)0.031 (3)0.006 (3)
N10.063 (4)0.046 (4)0.023 (3)0.000 (3)0.007 (3)−0.002 (3)
N20.088 (5)0.057 (4)0.044 (4)0.014 (4)0.039 (4)0.011 (4)
C10.065 (5)0.058 (6)0.025 (4)0.012 (5)0.010 (3)0.001 (4)
C20.068 (5)0.063 (6)0.038 (5)0.015 (5)0.008 (4)−0.008 (4)
C30.089 (6)0.045 (5)0.044 (5)0.006 (5)0.005 (5)−0.004 (4)
C40.077 (5)0.042 (5)0.037 (4)−0.002 (5)0.012 (4)0.000 (4)
C50.061 (5)0.038 (4)0.024 (4)−0.005 (4)0.009 (3)0.003 (3)
C60.057 (5)0.038 (4)0.032 (4)−0.007 (4)0.020 (3)−0.006 (4)

Geometric parameters (Å, °)

Br—C11.905 (8)C2—C31.349 (12)
O—C61.235 (8)C2—H2C0.9300
N1—C11.322 (9)C3—C41.362 (12)
N1—C51.342 (9)C3—H3A0.9300
N2—C61.303 (10)C4—C51.361 (10)
N2—H2A0.8600C4—H4A0.9300
N2—H2B0.8600C5—C61.503 (10)
C1—C21.360 (11)
C1—N1—C5115.1 (6)C2—C3—H3A119.8
C6—N2—H2A120.0C4—C3—H3A119.8
C6—N2—H2B120.0C5—C4—C3118.1 (8)
H2A—N2—H2B120.0C5—C4—H4A121.0
N1—C1—C2125.6 (8)C3—C4—H4A121.0
N1—C1—Br115.0 (6)N1—C5—C4123.6 (7)
C2—C1—Br119.4 (6)N1—C5—C6115.1 (6)
C3—C2—C1117.0 (8)C4—C5—C6121.4 (7)
C3—C2—H2C121.5O—C6—N2123.6 (7)
C1—C2—H2C121.5O—C6—C5118.5 (7)
C2—C3—C4120.4 (8)N2—C6—C5117.8 (6)
C5—N1—C1—C24.5 (11)C1—N1—C5—C6176.1 (6)
C5—N1—C1—Br−175.2 (5)C3—C4—C5—N10.2 (12)
N1—C1—C2—C3−0.9 (13)C3—C4—C5—C6−179.9 (7)
Br—C1—C2—C3178.7 (6)N1—C5—C6—O−154.5 (7)
C1—C2—C3—C4−3.3 (13)C4—C5—C6—O25.5 (11)
C2—C3—C4—C53.6 (13)N1—C5—C6—N225.3 (10)
C1—N1—C5—C4−4.0 (10)C4—C5—C6—N2−154.6 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···N10.862.412.730 (10)102
N2—H2A···Oi0.861.992.849 (9)176
N2—H2B···Oii0.862.223.002 (9)151

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5211).

References

  • Altmann, E. & Aichholz, R. (2007). J. Med. Chem. 50, 591–594. [PubMed]
  • Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft. The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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