1-(3-Chloro-pyridin-2-yl)hydrazine.

The title compound, C(5)H(6)ClN(3), was synthesized by the reaction of 2,3-dichloro-pyridine and hydrazine hydrate. An intra-molecular N-H⋯Cl hydrogen bond results in the formation of a planar (mean deviation 0.038 Å) five-membered ring. In the crystal, inter-molecular N-H⋯N hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

The title compound is an inter­mediate in the synthesis of Rynaxypyr, a new insecticidal anthranilic diamide. For the synthesis and biological properties of Rynaxypyr, see: Lahm et al. (2007 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C5H6ClN3

M = 143.58

Monoclinic,

a = 11.637 (2) Å

b = 3.9060 (8) Å

c = 13.946 (3) Å

β = 103.46 (3)°

V = 616.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.52 mm−1

T = 293 K

0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.860, T max = 0.950

2173 measured reflections

1124 independent reflections

936 reflections with I > 2σ(I)

R int = 0.036

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.082

S = 1.04

1124 reflections

91 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.15 e Å−3

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: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036950/im2217sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036950/im2217Isup2.hkl

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

C5H6ClN3	F(000) = 296
Mr = 143.58	Dx = 1.547 Mg m−3
Monoclinic, P21/c	Melting point = 427–429 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.637 (2) Å	Cell parameters from 25 reflections
b = 3.9060 (8) Å	θ = 9–13°
c = 13.946 (3) Å	µ = 0.52 mm−1
β = 103.46 (3)°	T = 293 K
V = 616.5 (2) Å3	Block, yellow
Z = 4	0.30 × 0.20 × 0.10 mm

Enraf–Nonius CAD-4 diffractometer	936 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
graphite	θmax = 25.3°, θmin = 1.8°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = −4→4
Tmin = 0.860, Tmax = 0.950	l = −16→16
2173 measured reflections	3 standard reflections every 200 reflections
1124 independent reflections	intensity decay: 1%

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0422P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
1124 reflections	Δρmax = 0.17 e Å−3
91 parameters	Δρmin = −0.15 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.166 (16)

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
Cl	0.18715 (4)	0.20164 (13)	0.95683 (4)	0.0436 (2)
N1	0.33408 (13)	0.6634 (4)	1.20853 (11)	0.0332 (4)
N2	0.41097 (14)	0.4864 (5)	1.07771 (12)	0.0394 (4)
H2A	0.4020 (19)	0.408 (6)	1.0174 (17)	0.059*
N3	0.51985 (14)	0.6524 (5)	1.11726 (13)	0.0388 (4)
H3B	0.509 (2)	0.874 (7)	1.1298 (17)	0.058*
H3A	0.554 (2)	0.586 (6)	1.1821 (16)	0.058*
C1	0.11354 (17)	0.4002 (5)	1.11712 (14)	0.0374 (5)
H1	0.0399	0.3118	1.0866	0.045*
C2	0.13219 (17)	0.5562 (5)	1.21092 (14)	0.0408 (5)
H2	0.0716	0.5732	1.2439	0.049*
C3	0.24223 (18)	0.6808 (5)	1.25120 (15)	0.0377 (5)
H3	0.2545	0.7854	1.3127	0.045*
C4	0.31800 (15)	0.5159 (4)	1.12028 (13)	0.0286 (4)
C5	0.20482 (16)	0.3823 (5)	1.07282 (13)	0.0307 (4)

	U11	U22	U33	U12	U13	U23
Cl	0.0486 (3)	0.0455 (3)	0.0348 (3)	−0.0082 (2)	0.0057 (2)	−0.0066 (2)
N1	0.0373 (9)	0.0332 (9)	0.0296 (8)	0.0007 (7)	0.0089 (7)	−0.0007 (7)
N2	0.0337 (9)	0.0518 (11)	0.0339 (9)	−0.0069 (8)	0.0103 (7)	−0.0107 (8)
N3	0.0334 (9)	0.0437 (10)	0.0392 (9)	−0.0045 (8)	0.0083 (7)	−0.0041 (8)
C1	0.0358 (10)	0.0331 (11)	0.0436 (11)	−0.0017 (8)	0.0095 (9)	0.0098 (9)
C2	0.0415 (11)	0.0414 (12)	0.0445 (12)	0.0053 (9)	0.0202 (9)	0.0071 (10)
C3	0.0481 (12)	0.0333 (10)	0.0348 (10)	0.0054 (9)	0.0158 (9)	0.0014 (8)
C4	0.0323 (10)	0.0231 (9)	0.0304 (9)	0.0017 (7)	0.0072 (7)	0.0026 (7)
C5	0.0365 (10)	0.0251 (9)	0.0292 (9)	0.0009 (8)	0.0048 (8)	0.0031 (7)

Cl—C5	1.7327 (18)	C1—C5	1.349 (3)
N1—C4	1.332 (2)	C1—C2	1.413 (3)
N1—C3	1.341 (2)	C1—H1	0.9300
N2—C4	1.355 (2)	C2—C3	1.363 (3)
N2—N3	1.416 (2)	C2—H2	0.9300
N2—H2A	0.88 (2)	C3—H3	0.9300
N3—H3B	0.90 (3)	C4—C5	1.428 (2)
N3—H3A	0.94 (2)
C4—N1—C3	118.50 (17)	C3—C2—H2	121.2
C4—N2—N3	121.60 (16)	C1—C2—H2	121.2
C4—N2—H2A	121.3 (15)	N1—C3—C2	124.65 (19)
N3—N2—H2A	115.4 (15)	N1—C3—H3	117.7
N2—N3—H3B	111.6 (15)	C2—C3—H3	117.7
N2—N3—H3A	112.9 (14)	N1—C4—N2	119.14 (16)
H3B—N3—H3A	97.2 (19)	N1—C4—C5	120.15 (16)
C5—C1—C2	118.59 (18)	N2—C4—C5	120.69 (16)
C5—C1—H1	120.7	C1—C5—C4	120.56 (17)
C2—C1—H1	120.7	C1—C5—Cl	120.90 (15)
C3—C2—C1	117.55 (18)	C4—C5—Cl	118.54 (14)
C5—C1—C2—C3	0.1 (3)	C2—C1—C5—C4	0.5 (3)
C4—N1—C3—C2	0.3 (3)	C2—C1—C5—Cl	−178.77 (13)
C1—C2—C3—N1	−0.6 (3)	N1—C4—C5—C1	−0.8 (3)
C3—N1—C4—N2	−177.86 (17)	N2—C4—C5—C1	177.42 (18)
C3—N1—C4—C5	0.3 (3)	N1—C4—C5—Cl	178.52 (13)
N3—N2—C4—N1	−9.6 (3)	N2—C4—C5—Cl	−3.3 (2)
N3—N2—C4—C5	172.20 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl	0.88 (2)	2.58 (2)	2.970 (2)	108 (2)
N2—H2A···N3i	0.88 (2)	2.28 (2)	3.058 (3)	148 (2)
N3—H3A···N1ii	0.94 (2)	2.41 (2)	3.243 (3)	148 (2)
N3—H3B···N2iii	0.90 (2)	2.68 (2)	3.492 (3)	151 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl	0.88 (2)	2.58 (2)	2.970 (2)	108 (2)
N2—H2A⋯N3i	0.88 (2)	2.28 (2)	3.058 (3)	148 (2)
N3—H3A⋯N1ii	0.94 (2)	2.41 (2)	3.243 (3)	148 (2)
N3—H3B⋯N2iii	0.90 (2)	2.68 (2)	3.492 (3)	151 (2)

Symmetry codes: (i) ; (ii) ; (iii) .