6-Bromo­pyridine-2-carboxamide

Xue, F.; Ju, S.

doi:10.1107/S1600536809047114

organic compounds

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Volume 65| Part 12| December 2009| Page o3161

doi:10.1107/S1600536809047114

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6-Bromopyridine-2-carboxamide

Feng Xue ^a and Shen-gui Ju ^a ^*

^aCollege of Chemistry and Chemical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: jushengui@163.com

(Received 4 November 2009; accepted 7 November 2009; online 21 November 2009)

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 ).

Experimental

Crystal data

C₆H₅BrN₂O
M_r = 201.03
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.063
wR(F²) = 0.172
S = 1.01
1296 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1	0.86	2.41	2.730 (10)	102
N2—H2A⋯Oⁱ	0.86	1.99	2.849 (9)	176
N2—H2B⋯Oⁱⁱ	0.86	2.22	3.002 (9)	151
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Related literature top

For medicinal background, see: Altmann et al. (2007).

Experimental top

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.

Computing details top

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

Figures top

	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.

6-Bromopyridine-2-carboxamide top

Crystal data top

C₆H₅BrN₂O	F(000) = 392
M_r = 201.03	D_x = 1.877 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 417 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.034 (3) Å	Cell parameters from 25 reflections
b = 6.4050 (13) Å	θ = 9–12°
c = 8.5540 (17) Å	µ = 5.70 mm⁻¹
β = 94.85 (3)°	T = 293 K
V = 711.6 (2) Å³	Block, colourless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	756 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.063
Graphite monochromator	θ_max = 25.3°, θ_min = 1.6°
ω/2θ scans	h = −15→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.395, T_max = 0.599	l = −10→10
1354 measured reflections	3 standard reflections every 200 reflections
1296 independent reflections	intensity decay: 1%

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) = 0.172	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.095P)²] where P = (F_o² + 2F_c²)/3
1296 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₆H₅BrN₂O	V = 711.6 (2) Å³
M_r = 201.03	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.034 (3) Å	µ = 5.70 mm⁻¹
b = 6.4050 (13) Å	T = 293 K
c = 8.5540 (17) Å	0.20 × 0.10 × 0.10 mm
β = 94.85 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	756 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.063
T_min = 0.395, T_max = 0.599	3 standard reflections every 200 reflections
1354 measured reflections	intensity decay: 1%
1296 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.01	Δρ_max = 0.45 e Å⁻³
1296 reflections	Δρ_min = −0.57 e Å⁻³
91 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br	0.91125 (7)	0.18241 (18)	0.81361 (11)	0.0756 (5)
O	0.5752 (4)	0.0268 (9)	1.2691 (6)	0.0584 (15)
N1	0.7461 (5)	0.1078 (10)	0.9836 (6)	0.0440 (16)
N2	0.5728 (6)	0.2794 (11)	1.0883 (8)	0.061 (2)
H2A	0.5265	0.3491	1.1317	0.073*
H2B	0.5970	0.3260	1.0045	0.073*
C1	0.8216 (6)	0.0086 (14)	0.9207 (8)	0.049 (2)
C2	0.8389 (7)	−0.2007 (15)	0.9279 (9)	0.057 (2)
H2C	0.8929	−0.2615	0.8798	0.068*
C3	0.7743 (7)	−0.3160 (14)	1.0077 (10)	0.059 (2)
H3A	0.7813	−0.4605	1.0110	0.071*
C4	0.6990 (7)	−0.2223 (12)	1.0837 (9)	0.052 (2)
H4A	0.6566	−0.2999	1.1439	0.062*
C5	0.6875 (6)	−0.0119 (11)	1.0690 (7)	0.0408 (18)
C6	0.6063 (6)	0.1033 (13)	1.1493 (8)	0.0417 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0750 (7)	0.0972 (9)	0.0596 (7)	−0.0039 (6)	0.0341 (5)	0.0056 (6)
O	0.084 (4)	0.056 (3)	0.039 (3)	−0.012 (3)	0.031 (3)	0.006 (3)
N1	0.063 (4)	0.046 (4)	0.023 (3)	0.000 (3)	0.007 (3)	−0.002 (3)
N2	0.088 (5)	0.057 (4)	0.044 (4)	0.014 (4)	0.039 (4)	0.011 (4)
C1	0.065 (5)	0.058 (6)	0.025 (4)	0.012 (5)	0.010 (3)	0.001 (4)
C2	0.068 (5)	0.063 (6)	0.038 (5)	0.015 (5)	0.008 (4)	−0.008 (4)
C3	0.089 (6)	0.045 (5)	0.044 (5)	0.006 (5)	0.005 (5)	−0.004 (4)
C4	0.077 (5)	0.042 (5)	0.037 (4)	−0.002 (5)	0.012 (4)	0.000 (4)
C5	0.061 (5)	0.038 (4)	0.024 (4)	−0.005 (4)	0.009 (3)	0.003 (3)
C6	0.057 (5)	0.038 (4)	0.032 (4)	−0.007 (4)	0.020 (3)	−0.006 (4)

Geometric parameters (Å, º) top

Br—C1	1.905 (8)	C2—C3	1.349 (12)
O—C6	1.235 (8)	C2—H2C	0.9300
N1—C1	1.322 (9)	C3—C4	1.362 (12)
N1—C5	1.342 (9)	C3—H3A	0.9300
N2—C6	1.303 (10)	C4—C5	1.361 (10)
N2—H2A	0.8600	C4—H4A	0.9300
N2—H2B	0.8600	C5—C6	1.503 (10)
C1—C2	1.360 (11)

C1—N1—C5	115.1 (6)	C2—C3—H3A	119.8
C6—N2—H2A	120.0	C4—C3—H3A	119.8
C6—N2—H2B	120.0	C5—C4—C3	118.1 (8)
H2A—N2—H2B	120.0	C5—C4—H4A	121.0
N1—C1—C2	125.6 (8)	C3—C4—H4A	121.0
N1—C1—Br	115.0 (6)	N1—C5—C4	123.6 (7)
C2—C1—Br	119.4 (6)	N1—C5—C6	115.1 (6)
C3—C2—C1	117.0 (8)	C4—C5—C6	121.4 (7)
C3—C2—H2C	121.5	O—C6—N2	123.6 (7)
C1—C2—H2C	121.5	O—C6—C5	118.5 (7)
C2—C3—C4	120.4 (8)	N2—C6—C5	117.8 (6)

C5—N1—C1—C2	4.5 (11)	C1—N1—C5—C6	176.1 (6)
C5—N1—C1—Br	−175.2 (5)	C3—C4—C5—N1	0.2 (12)
N1—C1—C2—C3	−0.9 (13)	C3—C4—C5—C6	−179.9 (7)
Br—C1—C2—C3	178.7 (6)	N1—C5—C6—O	−154.5 (7)
C1—C2—C3—C4	−3.3 (13)	C4—C5—C6—O	25.5 (11)
C2—C3—C4—C5	3.6 (13)	N1—C5—C6—N2	25.3 (10)
C1—N1—C5—C4	−4.0 (10)	C4—C5—C6—N2	−154.6 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1	0.86	2.41	2.730 (10)	102
N2—H2A···Oⁱ	0.86	1.99	2.849 (9)	176
N2—H2B···Oⁱⁱ	0.86	2.22	3.002 (9)	151

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

Experimental details

Crystal data
Chemical formula	C₆H₅BrN₂O
M_r	201.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.034 (3), 6.4050 (13), 8.5540 (17)
β (°)	94.85 (3)
V (Å³)	711.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.70
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.395, 0.599
No. of measured, independent and observed [I > 2σ(I)] reflections	1354, 1296, 756
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.172, 1.01
No. of reflections	1296
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.57

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1	0.86	2.41	2.730 (10)	102
N2—H2A···Oⁱ	0.86	1.99	2.849 (9)	176
N2—H2B···Oⁱⁱ	0.86	2.22	3.002 (9)	151

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

References

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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3161

doi:10.1107/S1600536809047114

Open

access