2-Amino-6-{[(6-chloropyridin-3-yl)methyl](ethyl)amino}-1-methyl-5-nitro-4-phenyl-1,4-dihydro­pyridine-3-carbonitrile ethanol monosolvate

Chuan-Wen Sun; Yan-Xia Chen; Tian-Yan Liu

doi:10.1107/S1600536812011750

. 2012 Mar 24;68(Pt 4):o1146. doi: 10.1107/S1600536812011750

2-Amino-6-{[(6-chloropyridin-3-yl)methyl](ethyl)amino}-1-methyl-5-nitro-4-phenyl-1,4-dihydropyridine-3-carbonitrile ethanol monosolvate

Chuan-Wen Sun ^a,^*, Yan-Xia Chen ^a, Tian-Yan Liu ^a

PMCID: PMC3344090 PMID: 22606093

Abstract

In the title compound, C₂₁H₂₁ClN₆O₂·C₂H₆O, a member of the insecticidal active neonicotinoid group of compounds, the 1,4-dihydropyridine ring adopts a boat conformation. An intramolecular C—H⋯O hydrogen bond occurs while the components are linked by an N—H⋯O interaction. The crystal packing is stablized by O—H⋯N hydrogen bonds and C—H⋯O interactions.

Related literature

For the synthesis, see: Zhang et al. (2010 ▶). For the insectidal activity of nitenpyram [systematic name: (E)-N-(6-Chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovinylidenediamine], see: Elbert & Nauen (2000 ▶); Jeschke & Nauen (2008 ▶); Kashiwada (1996 ▶); Minamida et al. (1993 ▶); Shao et al. (2008 ▶); Tomizawa & Casida (2009 ▶).

Experimental

Crystal data

C₂₁H₂₁ClN₆O₂·C₂H₆O
M _r = 470.96
Orthorhombic,
a = 19.3334 (19) Å
b = 12.1156 (12) Å
c = 20.644 (2) Å
V = 4835.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS: Bruker, 2001 ▶) T _min = 0.970, T _max = 0.981
44471 measured reflections
4267 independent reflections
3044 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.135
S = 1.05
4267 reflections
330 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812011750/gg2077sup1.cif

e-68-o1146-sup1.cif^{(33.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011750/gg2077Isup2.hkl

e-68-o1146-Isup2.hkl^{(209.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812011750/gg2077Isup3.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
O3—H3A⋯N1ⁱ	0.82	1.97	2.785 (13)	179
N4—H4B⋯O3	0.86	2.26	2.902 (11)	132
C6—H6A⋯O2	0.97	2.13	2.783 (3)	124
C7—H7B⋯O2ⁱⁱ	0.97	2.57	3.378 (3)	141

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (21042010, 21102092 and 30870560).

supplementary crystallographic information

Comment

Neonicotinoid insecticides (NNSs), which act agonistically on the insect nicotinic acetylcholine receptors (nAChRs), are gaining widespread use as a way to control pests, because of their high potency and low mammalian toxicity. As part of the chloronicotinyl subclass, nitenpyram, which was brought to the market two decades ago, also showed higher selectivity and better systemic properties against mammals, birds, aquatic life than insects, due to the differential binding affinities with the nAChR receptors of their neurosystem. (Jeschke & Nauen, 2008; Tomizawa & Casida, 2009; Minamida et al., 1993; Kashiwada, 1996; Shao et al., 2008; Elbert & Nauen, 2000). In this report, the title compound (Scheme I) was synthesized and characterized by X-ray diffraction.

In the title structure, C₂₁H₂₁ClN₆O₂C₂H₆O, (I), there is a cis-2-Amino-6-[N-(6-chloro-3-pyridinylmethyl)-N-ethyl]amino-3-cyano-1-methyl-5- nitro-4-phenyl-1,4-dihydropyridine molecule and a ethanol molecule in the asymmetric unit (Fig. 1). The 1,4-dihydropyridine ring adopts a sofa (boat) conformation. As compared with the trans configuration of nitro in the crystal structure of nitenpyram, the nitro group in the title compound is in the cis configuration as anticipated. Interestingly, the C–C and C-N bond length data (C9–N3 1.389 (2) Å, N3–C10 1.402 (3) Å, C11–C12 1.510 (3) Å and C12-C13 1.519 (3) Å) in the structure of (I) are shorter than the standard C–C (1.54 Å) and C–N (1.47 Å). On the contrary, the C═C bond length data (C9═C13 1.384 (3) Å and C10═C11 1.348 (3) Å) are longer than the standard C═C bond (1.34 Å). This shows that there is a homo-conjugation effect on the 1,4-dihydropyridine scaffold (Fig. 1).

The crystal packing is stablized by O-H···N, N-H···O and C-H···O hydrogen bonds (Fig. 2). Analysis shows that no intermolecular p···π or C-H···π interactions exist in the crystal structure.

Experimental

The title compound was prepared by the literature method (Zhang et al., 2010) and it was obtained using volatilization of petroleum ether and ethanol solution at room temperature, giving yellow crystals (yield 83.7%). ¹H NMR (CDCl₃, 400 Hz): 8.08 (d, J = 12.4 Hz,1H, Py—H), 7.34 (d, J = 8.9 Hz, 1H, Py—H), 7.24 (s,3H,Ph—H), 7.08 (m, J = 7.8 Hz, 1H, Py—H), 7.05–6.95 (m, 2H, Ph—H), 5.06 (s, 1H, CH), 4.79 (s, 2H, NH₂), 4.33 (d, J = 14.8 Hz, 1H), 4.06 (m, J = 14.6 Hz, 1H), 3.35–3.20 (m, 1H), 3.17 (s, 3H, NCH₃), 3.10 (d, J = 7.3 Hz,1H), 1.33–1.21 (m,3H,NCH₂CH₃). IR(KBr, cm^-1) 2974 (CH₃), 3327, 3197 (NH₂), 2184 (CN), 1457, 1409 (NO₂), 1648, 1614, 1557 (benzene).Anal. calcd. for C₂₃H₂₁ClN₆O₂ C 59.36, H 4.98, N 19.78% found, C 59.38, H 4.97, N 19.76%.