2-Chloro-5-(chloro­meth­yl)pyridine

Feng, Z.-Q.; Yang, X.-L.; Ye, Y.-F.; Wang, H.-Q.; Hao, L.-Y.

doi:10.1107/S1600536811000821

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o366

doi:10.1107/S1600536811000821

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2-Chloro-5-(chloromethyl)pyridine

Zhi-Qiang Feng,^a ^* Xiao-Li Yang,^a Yuan-Feng Ye,^a Huai-Qing Wang ^a and Ling-Yun Hao ^a

^aSchool of Material Engineering, Jinling Institute of Technology, Nanjing 211169, People's Republic of China
^*Correspondence e-mail: fzq@jit.edu.cn

(Received 23 December 2010; accepted 6 January 2011; online 12 January 2011)

The title compound, C₆H₅Cl₂N, is almost planar, with an r.m.s. deviation of 0.0146 Å for all atoms except for the 5-choloromethyl Cl atom. The offset Cl atom lies above this plane with a Cl—C—C angle of 111.11 (17)°. In the crystal, molecules are connected via intermolecular C—H⋯N hydrogen bonds, forming dimers.

Related literature

For the synthetic procedure, see: Nishihara et al. (1993 ). For bond-length data, see: Allen et al. (1987 ). The title compound is an intermediate in the synthesis of imidacloprid [systematic name (E)-1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine], see: Shroff et al. (2007 ).

Experimental

Crystal data

C₆H₅Cl₂N
M_r = 162.01
Monoclinic, P 2₁ /c
a = 4.0770 (8) Å
b = 10.322 (2) Å
c = 16.891 (3) Å
β = 95.95 (3)°
V = 707.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.791, T_max = 0.853
2886 measured reflections
1299 independent reflections
1028 reflections with I > 2σ(I)
R_int = 0.049
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.129
S = 1.00
1299 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯Nⁱ	0.97	2.57	3.453 (3)	151
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; 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 I, global. DOI: 10.1107/S1600536811000821/bq2267sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000821/bq2267Isup2.hkl

checkCIF report

Comment top

The tittle compound, 2-chloro-5-(chloromethyl)pyridine (I), is an important intermediate for the synthesis of imidacloprid (Shroff et al., 2007) and we report here its crystal structure.

The molecular structure of (I) is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987). In the crystal structure, the molecules were connected together via weak C—H···N intermolecular hydrogen bonds forming dimers, which seems to be effective in the stabilization of the crystal structure.

Related literature top

For the synthetic procedure, see: Nishihara et al. (1993). For bond-length data, see: Allen et al. (1987). The title compound is an intermediate in the synthesis of imidacloprid [systematic name (E)-1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine], see: Shroff et al. (2007).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Nishihara et al., 1993). The crystals were obtained by dissolving (I) (0.2 g, 1.2 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 5 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); 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. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I). C—H···N hydrogen bonds are shown by dashed lines.

2-Chloro-5-(chloromethyl)pyridine top

Crystal data top

C₆H₅Cl₂N	F(000) = 328
M_r = 162.01	D_x = 1.522 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 4.0770 (8) Å	θ = 10–14°
b = 10.322 (2) Å	µ = 0.82 mm⁻¹
c = 16.891 (3) Å	T = 293 K
β = 95.95 (3)°	Block, colorless
V = 707.0 (2) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1028 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.049
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = 0→4
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
T_min = 0.791, T_max = 0.853	l = −20→20
2886 measured reflections	3 standard reflections every 200 reflections
1299 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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.090P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1299 reflections	Δρ_max = 0.19 e Å⁻³
83 parameters	Δρ_min = −0.18 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: 0.025 (5)

Crystal data top

C₆H₅Cl₂N	V = 707.0 (2) Å³
M_r = 162.01	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.0770 (8) Å	µ = 0.82 mm⁻¹
b = 10.322 (2) Å	T = 293 K
c = 16.891 (3) Å	0.30 × 0.20 × 0.20 mm
β = 95.95 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1028 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.049
T_min = 0.791, T_max = 0.853	3 standard reflections every 200 reflections
2886 measured reflections	intensity decay: 1%
1299 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.00	Δρ_max = 0.19 e Å⁻³
1299 reflections	Δρ_min = −0.18 e Å⁻³
83 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
N	0.1376 (5)	0.3311 (2)	0.19100 (11)	0.0614 (5)
Cl1	0.2101 (2)	0.54073 (7)	0.11039 (4)	0.0867 (4)
C1	0.1642 (6)	0.2038 (2)	0.20387 (12)	0.0573 (6)
H1A	0.0900	0.1710	0.2501	0.069*
Cl2	0.11280 (19)	−0.12135 (6)	0.09764 (4)	0.0757 (3)
C2	0.2433 (6)	0.3739 (2)	0.12537 (14)	0.0559 (6)
C3	0.3774 (7)	0.2985 (2)	0.06990 (14)	0.0598 (6)
H3A	0.4474	0.3344	0.0240	0.072*
C4	0.4038 (6)	0.1686 (2)	0.08483 (13)	0.0558 (6)
H4A	0.4954	0.1144	0.0491	0.067*
C5	0.2944 (5)	0.1178 (2)	0.15315 (12)	0.0490 (5)
C6	0.3244 (6)	−0.0224 (2)	0.17406 (15)	0.0621 (6)
H6A	0.2322	−0.0375	0.2239	0.075*
H6B	0.5556	−0.0464	0.1812	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0734 (14)	0.0648 (12)	0.0481 (10)	−0.0050 (10)	0.0169 (9)	−0.0118 (9)
Cl1	0.1250 (8)	0.0567 (4)	0.0825 (6)	0.0007 (4)	0.0292 (5)	−0.0030 (3)
C1	0.0626 (14)	0.0737 (14)	0.0374 (11)	−0.0081 (12)	0.0137 (10)	−0.0006 (9)
Cl2	0.0946 (6)	0.0576 (4)	0.0772 (5)	−0.0046 (3)	0.0203 (4)	−0.0059 (3)
C2	0.0645 (14)	0.0562 (13)	0.0477 (11)	−0.0062 (10)	0.0089 (11)	−0.0047 (9)
C3	0.0761 (16)	0.0632 (13)	0.0426 (11)	−0.0057 (12)	0.0187 (11)	0.0020 (10)
C4	0.0640 (14)	0.0614 (13)	0.0444 (12)	0.0020 (11)	0.0166 (10)	−0.0048 (9)
C5	0.0445 (11)	0.0614 (12)	0.0410 (10)	−0.0022 (10)	0.0044 (9)	0.0011 (9)
C6	0.0638 (15)	0.0686 (14)	0.0545 (13)	0.0052 (12)	0.0088 (11)	0.0120 (11)

Geometric parameters (Å, º) top

N—C2	1.307 (3)	C3—C4	1.367 (3)
N—C1	1.334 (3)	C3—H3A	0.9300
Cl1—C2	1.743 (3)	C4—C5	1.383 (3)
C1—C5	1.378 (3)	C4—H4A	0.9300
C1—H1A	0.9300	C5—C6	1.491 (3)
Cl2—C6	1.795 (3)	C6—H6A	0.9700
C2—C3	1.375 (3)	C6—H6B	0.9700

C2—N—C1	116.3 (2)	C3—C4—H4A	120.0
N—C1—C5	124.3 (2)	C5—C4—H4A	120.0
N—C1—H1A	117.9	C1—C5—C4	116.9 (2)
C5—C1—H1A	117.9	C1—C5—C6	120.3 (2)
N—C2—C3	125.1 (2)	C4—C5—C6	122.7 (2)
N—C2—Cl1	115.46 (18)	C5—C6—Cl2	111.11 (17)
C3—C2—Cl1	119.40 (18)	C5—C6—H6A	109.4
C4—C3—C2	117.3 (2)	Cl2—C6—H6A	109.4
C4—C3—H3A	121.3	C5—C6—H6B	109.4
C2—C3—H3A	121.3	Cl2—C6—H6B	109.4
C3—C4—C5	120.0 (2)	H6A—C6—H6B	108.0

C2—N—C1—C5	0.2 (4)	N—C1—C5—C4	0.1 (4)
C1—N—C2—C3	−0.1 (4)	N—C1—C5—C6	177.9 (2)
C1—N—C2—Cl1	−179.33 (18)	C3—C4—C5—C1	−0.6 (3)
N—C2—C3—C4	−0.4 (4)	C3—C4—C5—C6	−178.3 (2)
Cl1—C2—C3—C4	178.9 (2)	C1—C5—C6—Cl2	123.5 (2)
C2—C3—C4—C5	0.7 (4)	C4—C5—C6—Cl2	−58.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···Nⁱ	0.97	2.57	3.453 (3)	151

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅Cl₂N
M_r	162.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	4.0770 (8), 10.322 (2), 16.891 (3)
β (°)	95.95 (3)
V (Å³)	707.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.791, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	2886, 1299, 1028
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.129, 1.00
No. of reflections	1299
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.18

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), 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
C6—H6A···Nⁱ	0.97	2.57	3.453 (3)	151

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

This work was supported by Jinling Institute of Technology (No. JIT-N-201011). The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

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