2-Chloro­pyridine-3-carboxamide

Abstract

In the crystal structure of the title compound, C₆H₅ClN₂O, the dihedral angle between the pyridine ring and the carboxamine group is 63.88 (8)°. Inter­molecular N—H⋯N and N—H⋯O hydrogen bonds link the mol­ecules into a two-dimensional network.

Related literature

Details of applications of the title compound can be found in: Oda et al. (1993 ▶); Qin et al. (2001 ▶).

Experimental

Crystal data

• C₆H₅ClN₂O

• M _r = 156.57

• Monoclinic,

• a = 6.980 (5) Å

• b = 13.627 (9) Å

• c = 7.108 (5) Å

• β = 91.82 (5)°

• V = 675.8 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.49 mm⁻¹

• T = 293 (2) K

• 0.30 × 0.20 × 0.20 mm

Data collection

• Siemens SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.868, T _max = 0.909

• 2716 measured reflections

• 1188 independent reflections

• 1083 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.096

• S = 1.11

• 1188 reflections

• 92 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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: SHELXL97.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.21	3.003 (3)	154
N2—H2B⋯Oii	0.86	2.17	3.015 (3)	168

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The structure of 2-chloropyridine-3-carboxamide has attracted us owing to its fungicidal activities (Oda et al., 1993) and its application in coordination chemistry (Qin et al., 2001). The dihedral angles formed by the pyridine ring and the carboxamine group amount to 63.88 (8)° (Fig. 1). The molecules are connected via intermolecular N—H···N and N—H···O hydrogen bonding into layers, with H···N distances of 2.21 and O···H distances of 2.17 Å (Fig. 2 and Tab. 1).

Experimental

Ammonia (10 ml, 66 mmol, 25%) was added slowly to a solution of 2-chloropyridine-3-carbonyl chloride (4.0 g, 22 mmol) in THF (20 ml) at 0°C. The reaction mixture was allowed to warm up to room temperature and stirred for 1.5 h. The resulting mixture was dried under vacuum and washed with two 20 ml portions of THF. Then the solution was dried over anhydrous magnesium sulfate. The solvent was removed by vacuum, and the product was collected, yield: 1.93 g, 56%; m.p. 162.5°C. The crystal suitable for X-ray analysis was grown by slow evaporation of the solvent from a diethyl ether solution at 20°. Anal. Calcd for C₆H₅ClN₂O: C, 45.97; H, 3.14; N, 17.82%. Found: C, 46.03; H, 3.22; N, 17.89%.

Refinement

All H atoms were positioned with idealized geometry, with C—H = 0.96 and N—H = 0.86 Å, and were refined with U_iso(H) values set to 1.2 U_eq(C,N).

Figures

Fig. 1.

View of the molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Fig. 2.

Crystal structure of the title compound along [100] with intermolecular N—H···N and N—H···O hydrogen bonding shown as dashed lines.

Crystal data

C6H5ClN2O	F(000) = 320
Mr = 156.57	Dx = 1.539 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.980 (5) Å	Cell parameters from 1764 reflections
b = 13.627 (9) Å	θ = 2.9–26.9°
c = 7.108 (5) Å	µ = 0.49 mm−1
β = 91.82 (5)°	T = 293 K
V = 675.8 (8) Å3	Plate, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection

Siemens SMART CCD area-detector diffractometer	1188 independent reflections
Radiation source: fine-focus sealed tube	1083 reflections with I > 2σ(I)
graphite	Rint = 0.021
ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −8→6
Tmin = 0.868, Tmax = 0.909	k = −15→16
2716 measured reflections	l = −6→8

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034	H-atom parameters constrained
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0551P)2 + 0.1035P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max < 0.001
1188 reflections	Δρmax = 0.18 e Å−3
92 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.051 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.14993 (7)	0.10791 (4)	0.88571 (7)	0.0533 (2)
C1	0.3716 (2)	0.07827 (13)	0.7965 (2)	0.0349 (4)
N1	0.4064 (2)	−0.01655 (11)	0.7824 (2)	0.0446 (4)
O	0.5546 (2)	0.30761 (9)	0.8932 (2)	0.0507 (4)
C6	0.4574 (2)	0.25974 (12)	0.7786 (2)	0.0351 (4)
N2	0.3180 (2)	0.29749 (11)	0.6708 (2)	0.0446 (4)
H2A	0.2909	0.3589	0.6786	0.054*
H2B	0.2545	0.2606	0.5930	0.054*
C3	0.6760 (3)	0.12278 (14)	0.6910 (3)	0.0430 (5)
H3	0.7681	0.1692	0.6616	0.052*
C4	0.7153 (3)	0.02376 (16)	0.6735 (3)	0.0505 (5)
H4	0.8331	0.0026	0.6312	0.061*
C2	0.4989 (2)	0.15240 (12)	0.7524 (2)	0.0325 (4)
C5	0.5774 (3)	−0.04231 (14)	0.7198 (3)	0.0506 (6)
H5	0.6042	−0.1088	0.7071	0.061*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl	0.0357 (3)	0.0599 (4)	0.0647 (4)	−0.0034 (2)	0.0066 (2)	0.0116 (2)
C1	0.0347 (9)	0.0346 (9)	0.0350 (9)	−0.0023 (7)	−0.0060 (7)	0.0017 (7)
N1	0.0541 (10)	0.0302 (8)	0.0485 (9)	−0.0029 (7)	−0.0125 (8)	0.0009 (6)
O	0.0548 (9)	0.0356 (7)	0.0603 (9)	−0.0041 (6)	−0.0181 (7)	−0.0060 (6)
C6	0.0333 (9)	0.0319 (9)	0.0399 (9)	−0.0025 (7)	−0.0003 (7)	0.0020 (7)
N2	0.0456 (9)	0.0300 (8)	0.0573 (10)	0.0039 (6)	−0.0124 (8)	−0.0020 (7)
C3	0.0336 (10)	0.0493 (12)	0.0460 (10)	0.0009 (8)	−0.0022 (8)	−0.0017 (8)
C4	0.0431 (11)	0.0566 (13)	0.0512 (12)	0.0162 (9)	−0.0069 (9)	−0.0109 (9)
C2	0.0298 (9)	0.0335 (9)	0.0337 (9)	0.0002 (7)	−0.0051 (7)	−0.0002 (7)
C5	0.0649 (14)	0.0346 (10)	0.0509 (11)	0.0130 (9)	−0.0191 (10)	−0.0081 (8)

Geometric parameters (Å, °)

Cl—C1	1.738 (2)	N2—H2B	0.8600
C1—N1	1.319 (2)	C3—C4	1.383 (3)
C1—C2	1.388 (3)	C3—C2	1.385 (3)
N1—C5	1.334 (3)	C3—H3	0.9300
O—C6	1.230 (2)	C4—C5	1.366 (3)
C6—N2	1.324 (2)	C4—H4	0.9300
C6—C2	1.504 (3)	C5—H5	0.9300
N2—H2A	0.8600
N1—C1—C2	125.08 (18)	C4—C3—H3	120.2
N1—C1—Cl	115.07 (14)	C2—C3—H3	120.2
C2—C1—Cl	119.80 (14)	C5—C4—C3	118.6 (2)
C1—N1—C5	116.88 (16)	C5—C4—H4	120.7
O—C6—N2	123.86 (17)	C3—C4—H4	120.7
O—C6—C2	119.55 (15)	C3—C2—C1	116.34 (17)
N2—C6—C2	116.57 (15)	C3—C2—C6	120.00 (16)
C6—N2—H2A	120.0	C1—C2—C6	123.56 (16)
C6—N2—H2B	120.0	N1—C5—C4	123.49 (18)
H2A—N2—H2B	120.0	N1—C5—H5	118.3
C4—C3—C2	119.63 (19)	C4—C5—H5	118.3

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.21	3.003 (3)	154
N2—H2B···Oii	0.86	2.17	3.015 (3)	168

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