3-Chloro-pyridin-2-amine.

In the title compound, C(5)H(5)ClN(2), a by-product in the synthesis of ethyl 2-(3-chloro-pyridin-2-yl)-5-oxopyrazolidine-3-carboxyl-ate, the amine groups form inter-molecular hydrogen-bonding associations with pyridine N-atom acceptors, giving centrosymmetric cyclic dimers. Short inter-molecular Cl⋯Cl inter-actions [3.278 (3) Å] also occur.

Related literature

The title compound was isolated as a by-product in the preparation of ethyl 2-(3-chloro­pyridin-2-yl)-5-oxopyrazolidine-3-carboxyl­ate, an inter­mediate in the synthesis of the insecticide chlorantraniliprole (systematic name 3-bromo-N-[4-chloro-2-methyl-6-[(methyl­amino)carbon­yl]phen­yl]-1-(3-chloro-2-pyridin­yl)-1H-pyrazole-5-carboxamide), see: Lahm et al. (2005 ▶). For related structures, see: Chao et al. (1975 ▶); Anagnostis & Turnbull (1998 ▶); Hemamalini & Fun (2010 ▶).

Experimental

Crystal data

C5H5ClN2

M = 128.56

Monoclinic,

a = 11.149 (8) Å

b = 5.453 (4) Å

c = 9.844 (7) Å

β = 90.581 (12)°

V = 598.5 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.52 mm−1

T = 296 K

0.38 × 0.32 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.827, T max = 0.894

2778 measured reflections

1057 independent reflections

867 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.182

S = 1.05

1057 reflections

73 parameters

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013432/zs2107sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013432/zs2107Isup2.hkl

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

C5H5ClN2	F(000) = 264
Mr = 128.56	Dx = 1.427 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1473 reflections
a = 11.149 (8) Å	θ = 3.7–27.2°
b = 5.453 (4) Å	µ = 0.52 mm−1
c = 9.844 (7) Å	T = 296 K
β = 90.581 (12)°	Block, yellow
V = 598.5 (7) Å3	0.38 × 0.32 × 0.22 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	1057 independent reflections
Radiation source: fine-focus sealed tube	867 reflections with I > 2σ(I)
graphite	Rint = 0.048
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→11
Tmin = 0.827, Tmax = 0.894	k = −6→6
2778 measured reflections	l = −8→11

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.1147P)2 + 0.2179P] where P = (Fo2 + 2Fc2)/3
1057 reflections	(Δ/σ)max < 0.001
73 parameters	Δρmax = 0.57 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.89884 (8)	0.20978 (18)	0.46576 (10)	0.0821 (5)
N1	0.6085 (2)	0.5920 (5)	0.3676 (2)	0.0597 (7)
N2	0.6357 (3)	0.2720 (5)	0.5172 (3)	0.0716 (8)
H2A	0.5613	0.2836	0.5385	0.086*
H2B	0.6804	0.1628	0.5553	0.086*
C1	0.6825 (2)	0.4252 (5)	0.4237 (3)	0.0505 (7)
C2	0.8035 (2)	0.4167 (5)	0.3855 (3)	0.0535 (7)
C3	0.8465 (3)	0.5728 (6)	0.2897 (3)	0.0635 (8)
H3	0.9266	0.5667	0.2645	0.076*
C4	0.7692 (3)	0.7404 (7)	0.2306 (3)	0.0725 (10)
H4	0.7955	0.8481	0.1640	0.087*
C5	0.6520 (3)	0.7431 (6)	0.2735 (4)	0.0698 (9)
H5	0.6000	0.8571	0.2345	0.084*

	U11	U22	U33	U12	U13	U23
Cl1	0.0717 (7)	0.0833 (7)	0.0913 (8)	0.0322 (4)	0.0101 (5)	0.0145 (4)
N1	0.0545 (13)	0.0566 (14)	0.0681 (15)	0.0068 (11)	0.0018 (10)	0.0047 (11)
N2	0.0674 (16)	0.0602 (16)	0.088 (2)	0.0131 (12)	0.0194 (14)	0.0196 (13)
C1	0.0572 (14)	0.0411 (13)	0.0533 (15)	0.0036 (11)	0.0026 (11)	−0.0039 (11)
C2	0.0558 (15)	0.0510 (15)	0.0537 (15)	0.0099 (11)	0.0019 (11)	−0.0057 (12)
C3	0.0561 (15)	0.076 (2)	0.0583 (17)	−0.0019 (14)	0.0070 (13)	0.0002 (14)
C4	0.077 (2)	0.074 (2)	0.067 (2)	−0.0049 (15)	0.0047 (17)	0.0178 (15)
C5	0.073 (2)	0.0617 (19)	0.074 (2)	0.0057 (14)	−0.0054 (16)	0.0155 (15)

Cl1—C2	1.735 (3)	C2—C3	1.361 (4)
N1—C5	1.334 (4)	C3—C4	1.380 (4)
N1—C1	1.344 (4)	C3—H3	0.9300
N2—C1	1.351 (4)	C4—C5	1.378 (5)
N2—H2A	0.8600	C4—H4	0.9300
N2—H2B	0.8600	C5—H5	0.9300
C1—C2	1.405 (4)
C5—N1—C1	118.5 (3)	C2—C3—C4	118.9 (3)
C1—N2—H2A	120.0	C2—C3—H3	120.6
C1—N2—H2B	120.0	C4—C3—H3	120.6
H2A—N2—H2B	120.0	C5—C4—C3	117.9 (3)
N1—C1—N2	117.3 (3)	C5—C4—H4	121.0
N1—C1—C2	120.0 (2)	C3—C4—H4	121.0
N2—C1—C2	122.7 (2)	N1—C5—C4	124.0 (3)
C3—C2—C1	120.7 (3)	N1—C5—H5	118.0
C3—C2—Cl1	120.2 (2)	C4—C5—H5	118.0
C1—C2—Cl1	119.0 (2)
C5—N1—C1—N2	−179.0 (3)	C1—C2—C3—C4	0.1 (5)
C5—N1—C1—C2	1.5 (4)	Cl1—C2—C3—C4	−178.0 (2)
N1—C1—C2—C3	−1.3 (4)	C2—C3—C4—C5	0.9 (5)
N2—C1—C2—C3	179.2 (3)	C1—N1—C5—C4	−0.6 (5)
N1—C1—C2—Cl1	176.8 (2)	C3—C4—C5—N1	−0.7 (5)
N2—C1—C2—Cl1	−2.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.22	3.051 (5)	162
N2—H2B···Cl1	0.86	2.61	3.001 (4)	109

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.22	3.051 (5)	162

Symmetry code: (i) .