(E)-2-{1-[(6-Chloro­pyridin-3-yl)meth­yl]imidazolidin-2-yl­idene}-2-cyano-N-(2-methylphenyl)acetamide

Jian Wu

doi:10.1107/S1600536811037524

. 2011 Sep 30;67(Pt 10):o2697. doi: 10.1107/S1600536811037524

(E)-2-{1-[(6-Chloropyridin-3-yl)methyl]imidazolidin-2-ylidene}-2-cyano-N-(2-methylphenyl)acetamide

Jian Wu ^a,^*

PMCID: PMC3201308 PMID: 22065122

Abstract

In the title compound, C₁₉H₁₈N₅O, the imidazolidine ring makes dihedral angles of 87.62 (17) and 28.27 (11)° with the pyridine and benzene rings, respectively. An intramolecular N—H⋯O hydrogen bond is observed between the carbonyl O atom and an imidazolidine H atom. In the crystal, an intermolecular N—H⋯N hydrogen bond gives rise to a linear chain running along the b axis.

Related literature

For background to neonicotinoids and their biological activity, see: Shao et al. (2008 ▶); Nishimura et al. (1994 ▶); Mori et al. (2002 ▶); Ohno et al. (2009 ▶); Tomizawa et al. (2000 ▶); Wu et al. (2011 ▶).

Experimental

Crystal data

C₁₉H₁₈ClN₅O
M _r = 367.83
Monoclinic,
a = 16.2019 (18) Å
b = 7.6240 (9) Å
c = 14.7368 (18) Å
β = 97.007 (3)°
V = 1806.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) ▶ T _min = 0.943, T _max = 0.953
19209 measured reflections
3512 independent reflections
2618 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.139
S = 1.03
3512 reflections
238 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037524/ng5220sup1.cif

e-67-o2697-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037524/ng5220Isup2.hkl

e-67-o2697-Isup2.hkl^{(168.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037524/ng5220Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811037524/ng5220Isup4.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N4ⁱ	0.86	2.49	3.044 (3)	123
N3—H3A⋯O1	0.86	2.07	2.659 (2)	126

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Symmetry code: (i) Inline graphic .

Acknowledgments

The author gratefully acknowledges the National Natural Science Foundation of China (Nos 20872021 and 21162004) and the Agricultural Scientific and Technological Project of Guizhou Province (No. 20103068) for financial support. The author also acknowledges the assistance of Professor Q. L. Zhang of Guiyang Medical University.

supplementary crystallographic information

Comment

Neonicotinoids, an interesting class of insecticide known to act on the central nervous system of insects, are widely used in agriculture due to their broad spectrum activity and low mammalian toxicity. As a part of our ongoing investigation of neonicotinoids analogs, we presented a series of neonicotinoid analogs bearing amide moieties that exhibit good activity against Nilaparvata lugens at 100 mg/L (Wu et al., 2011). However,the accurate configuration of the active compound in our previous work has not been reported. Herein, we report the crystal structure of the title compound, (E)-2-(1-((6-chloropyridin-3-yl)methyl)imidazolidin-2-ylidene)-2- cyano-N-(o-tolyl)acetamide. It is noteworthy that the crystal of neonicotinoid analog bearing an amide moiety was obtained for the first time.

In the molecule of the title compound (Fig. 1), the imidazoline ring makes dihedral angles of 87.62 (17) ° with pyridine ring and 28.27 (11) ° with benzene ring. An intramolecular N—H···O hydrogen bond is observed between the O atom of carbonyl and imidazoline H atom; The ststructure possesses an intramolecular N3—H3A···O1 hydrogen bond with N3—H3A = 0.86 Å, H3A—O1 = 2.0661 Å, N3—O1 = 2.659 (2) Å, and N—H···O = 125.44 °. In the crystal structure, there are N3—H3A···N4ⁱ hydrogen bonds and C—H···π interactions between neighboring molecules, which with the length for bonds N3—H3A, H3A—N4, H3A—N4 were 0.86 Å, 2.4883 Å, 3.044 (3) Å and the angles for N—H···N, C8—H8B···Cg(2)ⁱⁱ were 123.03 ° and 113.20 °, respectively; Furthermore, the length for H8B···Cg(2)ⁱⁱ and C8···Cg(2)ⁱⁱ were 3.1386 Å and 3.632 (3) Å, the angle of C19—H12A···Cg(3)ⁱⁱⁱ is 130.96 °; In addition, the length of H12A···Cg(3)ⁱⁱⁱ and C19···Cg(3)ⁱⁱⁱ were 3.0384 Å and 3.827 (3) Å, respectively [symmetry codes: (i) x,-1 + y,z, (ii) x,-1 + y,z, (iii) x,1 - y,1 - z].

Experimental

A mixture of 2-cyano-3,3-bis(methylthio)-N-(o-tolyl)acrylamide (1 mmol) and N-((6-chloropyridin-3-yl) methyl) ethane-1,2-diamine (1 mmol) was stirred in refluxing ethanol (10 ml). The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was cooled to room temperature, block-shaped crystals were formed, which was filtered off, washed with ethanol and dried in the air.