1-(3-Chloro­pyridin-2-yl)hydrazine

Wang, P.; Wan, R.; Yu, P.; He, Q.; Zhang, J.

doi:10.1107/S1600536810036950

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2599

doi:10.1107/S1600536810036950

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1-(3-Chloropyridin-2-yl)hydrazine

Peng Wang,^a Rong Wan,^a ^* Peng Yu,^a Qiu He ^a and Jian-qiang Zhang ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 29 June 2010; accepted 15 September 2010; online 18 September 2010)

The title compound, C₅H₆ClN₃, was synthesized by the reaction of 2,3-dichloropyridine and hydrazine hydrate. An intramolecular N—H⋯Cl hydrogen bond results in the formation of a planar (mean deviation 0.038 Å) five-membered ring. In the crystal, intermolecular N—H⋯N hydrogen bonds link the molecules 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_r = 143.58
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 1.04
1124 reflections
91 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

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) -x+1, -y+1, -z+2; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (iii) x, y+1, z.

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.

Supporting information

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

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

checkCIF report

Comment top

1-(3-Chloropyridin-2-yl)hydrazine is an important intermediate in the synthesis of Rynaxypyr, a new insecticidal anthranilic diamide, which acts as a potent and selective ryanodine receptor activator. Rynaxypyr is characterized by its high levels of insecticidal activity and low toxicity to mammals attributed to a high selectivity for insect over mammalian ryanodine receptors (Lahm et al., 2007).

We report herein the crystal structure of the title compound,(I). In the molecule of the title compound (Fig. 1), bond lengths (Allen et al., 1987) and angles are within normal ranges. The pyridine ring A(C1/C2/C3/N1/C4/C5) is, of course, planar with a mean deviation from planarity of 0.0027 Å (C1 - 0.0013, C2 - 0.0027, C3 0.0037, N1 - 0.0005, C4 - 0.0034 and C5 0.0042 Å, respectively). An intramolecular N—H···Cl hydrogen bond (Table 1) results in the formation of one planar five-membered ring B(C4/C5/Cl/H2A/N2) with a mean deviation from planarity of 0.0380 Å (C4 0.0119, C5 - 0.0382, Cl 0.0382, H2A -0.0568 and N2 0.0503 Å, respectively). The dihedral angle A/B = 3.5 (1) Å, showing the rings to be almost coplanar. In the crystal structure, three intermolecular N—H···N hydrogen bonds (Table 1) link the molecules to form a three-dimensional network (Fig. 2).

Related literature top

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 top

Hydrazine hydrate (10 mmol) was added dropwise to a refluxing solution of 2,3-dichloropyridine (10 mmol) in ethanol. The reaction mixture was stirred and refluxed for 2 h. After cooling and filtering, crude compound (I) was obtained. Pure compound (I) was obtained by recrystallization from THF (15 ml, yield 65%). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an ethanolic 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dashed line.
	Fig. 2. Partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

1-(3-Chloropyridin-2-yl)hydrazine top

Crystal data top

C₅H₆ClN₃	F(000) = 296
M_r = 143.58	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0422P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
1124 reflections	Δρ_max = 0.17 e Å⁻³
91 parameters	Δρ_min = −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)

Crystal data top

C₅H₆ClN₃	V = 616.5 (2) Å³
M_r = 143.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.637 (2) Å	µ = 0.52 mm⁻¹
b = 3.9060 (8) Å	T = 293 K
c = 13.946 (3) Å	0.30 × 0.20 × 0.10 mm
β = 103.46 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	936 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.036
T_min = 0.860, T_max = 0.950	3 standard reflections every 200 reflections
2173 measured reflections	intensity decay: 1%
1124 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.17 e Å⁻³
1124 reflections	Δρ_min = −0.15 e Å⁻³
91 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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+2; (ii) −x+1, y−1/2, −z+5/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₅H₆ClN₃
M_r	143.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.637 (2), 3.9060 (8), 13.946 (3)
β (°)	103.46 (3)
V (Å³)	616.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.860, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	2173, 1124, 936
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 1.04
No. of reflections	1124
No. of parameters	91
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

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

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+2; (ii) −x+1, y−1/2, −z+5/2; (iii) x, y+1, z.

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for allowing the Enraf–Nonius CAD-4 diffractometer to be used for this research project.

References

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