Ethyl 2-{3-[(2-chloro-1,3-thia­zol-5-yl)meth­yl]-4-nitro­imino-1,3,5-triazinan-1-yl}acetate

Chuan-wen Sun; Jun Zhu; Jia Jin; Ding-rong Yang

doi:10.1107/S1600536810018878

. 2010 May 26;66(Pt 6):o1457–o1458. doi: 10.1107/S1600536810018878

Ethyl 2-{3-[(2-chloro-1,3-thiazol-5-yl)methyl]-4-nitroimino-1,3,5-triazinan-1-yl}acetate

Chuan-wen Sun ^a,^*, Jun Zhu ^a, Jia Jin ^a, Ding-rong Yang ^a

PMCID: PMC2979404 PMID: 21579526

Abstract

In the title compound, C₁₁H₁₅ClN₆O₄S, which belongs to the neonicotinoid class of insecticidally active heterocyclic compounds, the six-membered triazine ring adopts an opened envolope conformation. The planar nitro imine group [dihedral angle between nitro and imine groups = 1.07 (7)°] and the thiazole ring are oriented at a dihedral angle of 69.62 (8)°. A classical intramolecular N—H⋯O hydrogen bond is found in the molecular structure. Moreover, one classical intermolecular N—H⋯N and four non-classical C—H⋯O and C—H⋯N hydrogen bonds are also present in the crystal structure. Besides intermolecular hydrogen bonds, the Cl atom forms an intermolecular short contact [3.020 (2) Å] with one of the nitro O atoms.

Related literature

For general background to neonicotinoid compounds and their application as insecticides, see: Kagabu (1996 ▶); Kagabu et al. (2005 ▶); Tian et al. (2007 ▶); Tomizawa et al. (2000 ▶); Tomizawa & Yamamoto (1993 ▶); Zhang et al. (2004 ▶). For halogen bonding, see: Riley & Merz (2007 ▶). For the synthesis of the title compound, see: Maienfisch et al. (2001 ▶).

Experimental

Crystal data

C₁₁H₁₅ClN₆O₄S
M _r = 362.81
Triclinic,
a = 8.5066 (6) Å
b = 9.1114 (7) Å
c = 10.9071 (8) Å
α = 100.488 (2)°
β = 98.416 (3)°
γ = 101.281 (3)°
V = 800.55 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 298 K
0.40 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.857, T _max = 0.925
5350 measured reflections
3259 independent reflections
2670 reflections with I > 2σ(I)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.128
S = 1.05
3259 reflections
212 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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 datablocks I, global. DOI: 10.1107/S1600536810018878/rk2201sup1.cif

e-66-o1457-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018878/rk2201Isup2.hkl

e-66-o1457-Isup2.hkl^{(159.8KB, hkl)}

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⋯N6ⁱ	0.79 (2)	2.55 (2)	3.133 (2)	132 (2)
N3—H3A⋯O3	0.79 (2)	1.98 (2)	2.570 (2)	131 (2)
C3—H3C⋯O3ⁱⁱ	0.97	2.57	3.191 (3)	122
C5—H5A⋯N1ⁱⁱⁱ	0.97	2.61	3.449 (3)	144
C6—H6B⋯O4^iv	0.97	2.56	3.478 (3)	159
C10—H10⋯O1^v	0.93	2.45	3.278 (3)	149

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This work was supported by the Innovation Program of Shanghai Municipal Education Commission (Ssd08013 and 09YZ157) and the Leading Academic Discipline Project of Shanghai Normal University (DZL808). We are also grateful for the support from the Key Scientific and Technological Project of Shanghai Science and Technology Commission (0939191200).

supplementary crystallographic information

Comment

Neonicotinoid compounds (Tomizawa & Yamamoto, 1993; Kagabu, 1996; Tomizawa et al., 2000) have received much attention on their applications as insecticide (Zhang et al., 2004; Kagabu et al., 2005; Tian et al., 2007). We report here the molecular and crystal structures of the title compound.

The molecular structure of title compound, C₁₁H₁₅ClN₆O₄S, is depicted on Fig.1. The triazine moiety exhibits an opened envolope conformation with N1 out of the envolope plan defined by C5, N3, C7, N2 and C6. The dihedral angle between the thiazole ring and triazine envolope plan is 75.63 (7)°. The planar nitroimine–group and the thiazole ring are oriented the dihedral angle of 69.62 (8)°. The large discrepancy between (O4—N5···N4 115.65 (17)°) and (O3—N5···N4 123.84 (16)°) bond angles attributes to the hydrogen bond effect on O4 and O3 - look the Table 1. Another interesting structure feature that should be mentioned is that the bond lengths (C7—N2 1.340 (2)Å) and (C7—N3 1.329 (2)Å) are between the standard (C—N 1.47Å) single bond and (C═N 1.26Å) double bond, clearly showing the conjugated effect of the nirtoimine. The C7—N4 bond length is as long as to 1.357 (2)Å, due to being linked with a strong electron–attracting nitro–group. Moreover, except intermolecular hydrogen bonding, the crystal structure is further stabilized by the so–called halogen bonding (Riley & Merz, 2007), due to short intermolecular contact of Cl1—O4ⁱ with a distance of 3.020 (2)Å and an angle close to 180° (C11—Cl1···O4ⁱ 178.1 (1)°). Symmetry code: (i) 1-x,1-y,-z).

Experimental

The title compound was prepared by the literature method (Maienfisch et al., (2001). It was purified by silica gel chromatography using ethyl acetate and petroleum ether in the ratio of 1:1, as the flush to afford. This compound was obtained as white crystals, yield 46.7%, ¹H NMR(CDCl₃, 400 Hz): 9.51 (1H, s, NH), 7.44 (1H, s, thiazole—H), 4.61 (2H,s,CH₂—thiazole), 4.48–4.49(4H, d, J = 5.2 Hz, triazine—4H), 4.21–4.15 (2H, m, OCH₂), 3.32 (2H, s, CHC═O) 1.29–1.26 (3H, t, J = 7.2 Hz, CH₃); IR(potassium bromide, cm^-1) 3288(N—H), 3000 (thiazole), 1730 (C═O) 1587 (C═N), 1398 (NO₂), 1224 (C—O—C), 1105 (C—N), Anal. calcd for C₁₁H₁₅ClN₆O₄S: C 36.42, H 4.17, N 23.16; found C 36.40, H 4.23, N 23.19. ESI–MS m/z: 363.8.