organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1138

3-Chloro­pyridin-2-amine

aDepartment of Chemistry, Liaoning University, Shenyang 110036, People's Republic of China, and bAgrochemicals Division, Shenyang Research Institute of Chemical Industry, Shenyang 110021, People's Republic of China
*Correspondence e-mail: libin1@sinochem.com

(Received 2 April 2011; accepted 11 April 2011; online 16 April 2011)

In the title compound, C5H5ClN2, a by-product in the synthesis of ethyl 2-(3-chloro­pyridin-2-yl)-5-oxopyrazolidine-3-carboxyl­ate, the amine groups form inter­molecular hydrogen-bonding associations with pyridine N-atom acceptors, giving centrosymmetric cyclic dimers. Short inter­molecular Cl⋯Cl inter­actions [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[Lahm, G. P., Selby, T. P. & Freudenberger, J. H. (2005). Bioorg. Med. Chem. Lett. 15, 4898-4906.]). For related structures, see: Chao et al. (1975[Chao, M., Schemp, E. & Rosenstein, R. D. (1975). Acta Cryst. B31, 2922-2924.]); Anagnostis & Turnbull (1998[Anagnostis, J. & Turnbull, M. M. (1998). Acta Cryst. C54, 681-683.]); Hemamalini & Fun (2010[Hemamalini, M. & Fun, H.-K. (2010). Acta Cryst. E66, o1416-o1417.]).

[Scheme 1]

Experimental

Crystal data
  • C5H5ClN2

  • Mr = 128.56

  • Monoclinic, P 21 /c

  • 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[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.827, Tmax = 0.894

  • 2778 measured reflections

  • 1057 independent reflections

  • 867 reflections with I > 2σ(I)

  • Rint = 0.048

Refinement
  • R[F2 > 2σ(F2)] = 0.059

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯N1i 0.86 2.22 3.051 (5) 162
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The structures of salts of the halo-substituted aminopyridine, such as 2-amino-5-chloropyridine-fumaric acid (Hemamalini & Fun, 2010), 2-amino-3,5-dichloropyridinium chloride monohydrate (Anagnostis & Turnbull, 1998), are known but the the structure of 2-amino-3-chloropyridine is not known. This compound, C5H5Cl1N2 (I) was isolated as a by-product in the preparation of ethyl 2-(3-chloropyridin-2-yl)-5-oxopyrazolidine-3-carboxylate, an important intermediate in the synthesis of the insecticide chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-[(methylamino) carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide) (Lahm et al., 2005). In the structure of (I) (Fig. 1), intermolecular amine N—H···Npyridine hydrogen-bonding interactions (Table 1) give centrosymmetric cyclic dimers (Fig. 2), similar to those found in the structure of 2-aminopyridine (Chao et al., 1975). In (I) there is an intramolecular N—H···Cl interaction [3.001 (3) Å] while in the crystal structure there are also short Cl···Clii interactions [3.278 (3) Å] [symmetry code: (ii) -x + 2, -y, -z + 1].

Related literature top

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 top

Sodium ethoxide (3.48 g, 50.4 mmol) and 150 ml of absolute ethanol was heated to reflux, after wich 6.80 g (47.4 mmol) of 3-chloro-2-hydrazinylpyridine was added and the mixture was allowed to reflux for 5 minutes. The slurry was then treated dropwise with 9.79 g (56.9 mmol) of diethyl maleate over a period of 5 minutes and the resulting solution was held at reflux for 10 minutes. After cooling to 338 K, the reaction mixture was treated with 5.0 ml (87.3 mmol) of glacial acetic acid. The mixture was diluted with 60 ml water and then cooled to room temperature, giving a precipitate which was isolated via filtration, and separated by column chromatography on silica gel (eluent: ethyl acetate/petroleum ether, 1:5). The title compound was obtained as a yellow solid (0.60 g, 8%) and recyrstallized from dichloromethane to afford colorless single crystals suitable for X-ray diffraction. Anal.: Calc. for C5H5Cl1N2: C, 46.47; H, 3.84; Cl, 27.96; N, 21.85%. Found: C, 46.71; H, 3.99; Cl, 27.58; N, 21.79. 1H NMR(CDCl3): 5.02(s,2H, NH2), 6.62(dd,1H, pyridine-H), 7.48(dd, 1H, pyridine-H), 7.98 (dd, 1H, pyridine-H).

Refinement top

Although all H atoms were visible in difference maps, they were placed in geometrically calculated positions, with N—H and C—H = o.86 and 0.93 Å respectively, and included in the final refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing atom numbering scheme and 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing of (I) in ther unit cell viewed down b, showing hydrogen-bonding interactions as dashed lines.
3-Chloropyridin-2-amine top
Crystal data top
C5H5ClN2F(000) = 264
Mr = 128.56Dx = 1.427 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1473 reflections
a = 11.149 (8) Åθ = 3.7–27.2°
b = 5.453 (4) ŵ = 0.52 mm1
c = 9.844 (7) ÅT = 296 K
β = 90.581 (12)°Block, yellow
V = 598.5 (7) Å30.38 × 0.32 × 0.22 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1057 independent reflections
Radiation source: fine-focus sealed tube867 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
ϕ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1311
Tmin = 0.827, Tmax = 0.894k = 66
2778 measured reflectionsl = 811
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182H-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 parametersΔρmax = 0.57 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C5H5ClN2V = 598.5 (7) Å3
Mr = 128.56Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.149 (8) ŵ = 0.52 mm1
b = 5.453 (4) ÅT = 296 K
c = 9.844 (7) Å0.38 × 0.32 × 0.22 mm
β = 90.581 (12)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1057 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
867 reflections with I > 2σ(I)
Tmin = 0.827, Tmax = 0.894Rint = 0.048
2778 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.182H-atom parameters constrained
S = 1.05Δρmax = 0.57 e Å3
1057 reflectionsΔρmin = 0.31 e Å3
73 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl10.89884 (8)0.20978 (18)0.46576 (10)0.0821 (5)
N10.6085 (2)0.5920 (5)0.3676 (2)0.0597 (7)
N20.6357 (3)0.2720 (5)0.5172 (3)0.0716 (8)
H2A0.56130.28360.53850.086*
H2B0.68040.16280.55530.086*
C10.6825 (2)0.4252 (5)0.4237 (3)0.0505 (7)
C20.8035 (2)0.4167 (5)0.3855 (3)0.0535 (7)
C30.8465 (3)0.5728 (6)0.2897 (3)0.0635 (8)
H30.92660.56670.26450.076*
C40.7692 (3)0.7404 (7)0.2306 (3)0.0725 (10)
H40.79550.84810.16400.087*
C50.6520 (3)0.7431 (6)0.2735 (4)0.0698 (9)
H50.60000.85710.23450.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0717 (7)0.0833 (7)0.0913 (8)0.0322 (4)0.0101 (5)0.0145 (4)
N10.0545 (13)0.0566 (14)0.0681 (15)0.0068 (11)0.0018 (10)0.0047 (11)
N20.0674 (16)0.0602 (16)0.088 (2)0.0131 (12)0.0194 (14)0.0196 (13)
C10.0572 (14)0.0411 (13)0.0533 (15)0.0036 (11)0.0026 (11)0.0039 (11)
C20.0558 (15)0.0510 (15)0.0537 (15)0.0099 (11)0.0019 (11)0.0057 (12)
C30.0561 (15)0.076 (2)0.0583 (17)0.0019 (14)0.0070 (13)0.0002 (14)
C40.077 (2)0.074 (2)0.067 (2)0.0049 (15)0.0047 (17)0.0178 (15)
C50.073 (2)0.0617 (19)0.074 (2)0.0057 (14)0.0054 (16)0.0155 (15)
Geometric parameters (Å, º) top
Cl1—C21.735 (3)C2—C31.361 (4)
N1—C51.334 (4)C3—C41.380 (4)
N1—C11.344 (4)C3—H30.9300
N2—C11.351 (4)C4—C51.378 (5)
N2—H2A0.8600C4—H40.9300
N2—H2B0.8600C5—H50.9300
C1—C21.405 (4)
C5—N1—C1118.5 (3)C2—C3—C4118.9 (3)
C1—N2—H2A120.0C2—C3—H3120.6
C1—N2—H2B120.0C4—C3—H3120.6
H2A—N2—H2B120.0C5—C4—C3117.9 (3)
N1—C1—N2117.3 (3)C5—C4—H4121.0
N1—C1—C2120.0 (2)C3—C4—H4121.0
N2—C1—C2122.7 (2)N1—C5—C4124.0 (3)
C3—C2—C1120.7 (3)N1—C5—H5118.0
C3—C2—Cl1120.2 (2)C4—C5—H5118.0
C1—C2—Cl1119.0 (2)
C5—N1—C1—N2179.0 (3)C1—C2—C3—C40.1 (5)
C5—N1—C1—C21.5 (4)Cl1—C2—C3—C4178.0 (2)
N1—C1—C2—C31.3 (4)C2—C3—C4—C50.9 (5)
N2—C1—C2—C3179.2 (3)C1—N1—C5—C40.6 (5)
N1—C1—C2—Cl1176.8 (2)C3—C4—C5—N10.7 (5)
N2—C1—C2—Cl12.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.862.223.051 (5)162
N2—H2B···Cl10.862.613.001 (4)109
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC5H5ClN2
Mr128.56
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)11.149 (8), 5.453 (4), 9.844 (7)
β (°) 90.581 (12)
V3)598.5 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.52
Crystal size (mm)0.38 × 0.32 × 0.22
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.827, 0.894
No. of measured, independent and
observed [I > 2σ(I)] reflections
2778, 1057, 867
Rint0.048
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.182, 1.05
No. of reflections1057
No. of parameters73
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.57, 0.31

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N1i0.862.223.051 (5)162
Symmetry code: (i) x+1, y+1, z+1.
 

References

First citationAnagnostis, J. & Turnbull, M. M. (1998). Acta Cryst. C54, 681–683.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationBruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChao, M., Schemp, E. & Rosenstein, R. D. (1975). Acta Cryst. B31, 2922–2924.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationHemamalini, M. & Fun, H.-K. (2010). Acta Cryst. E66, o1416–o1417.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLahm, G. P., Selby, T. P. & Freudenberger, J. H. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 5| May 2011| Page o1138
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