rac-1-(Furan-2-ylmeth­yl)-N-nitro-5-(oxolan-2-ylmeth­yl)-1,3,5-triazinan-2-imine

Chuan-Wen Sun; Xu-Bo Ma; Hong-Fei Bu

doi:10.1107/S1600536810036561

. 2010 Sep 18;66(Pt 10):o2581. doi: 10.1107/S1600536810036561

rac-1-(Furan-2-ylmethyl)-N-nitro-5-(oxolan-2-ylmethyl)-1,3,5-triazinan-2-imine

Chuan-Wen Sun ^a,^*, Xu-Bo Ma ^a, Hong-Fei Bu ^a

PMCID: PMC2983308 PMID: 21587563

Abstract

In the title compound C₁₃H₁₉N₅O₄, which belongs to the insecticidally active neonicotinoid group of compounds, the triazane ring exhibits a half-chair conformation. The large discrepancy between the two nitro O—N—N bond angles [116.1 (2) and 123.98 (19)°] may be attributed to intramolecular N—H⋯O hydrogen bonding involving one of the nitro O atoms as the acceptor. The delocalization of the electrons extends as far as the nitro group, forming coplanar π-electron networks. In the crystal, inversion dimers lined by pairs of N—H⋯O hydrogen bonds occur.

Related literature

For general background to neonicotinoids, see: Kagabu et al. (2005 ▶); Peter & Ralf (2008 ▶); Riley & Merz (2007 ▶); Tian et al. (2007 ▶); Tomizawa et al. (2000 ▶). For the synthesis, see: Zhu et al. (2010 ▶).

Experimental

Crystal data

C₁₃H₁₉N₅O₄
M _r = 309.33
Monoclinic,
a = 11.1898 (12) Å
b = 9.262 (1) Å
c = 14.4863 (15) Å
β = 99.276 (2)°
V = 1481.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
9196 measured reflections
2902 independent reflections
2615 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.164
S = 1.18
2902 reflections
202 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036561/zs2064sup1.cif

e-66-o2581-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036561/zs2064Isup2.hkl

e-66-o2581-Isup2.hkl^{(142.5KB, 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
N2—H2⋯O3	0.82 (3)	1.97 (3)	2.563 (3)	128 (2)
N2—H2⋯O1ⁱ	0.82 (3)	2.43 (3)	3.035 (3)	132 (2)

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

In recent years, the neonicotinoids have been the fastest-growing class of insecticides used in modern crop protection (Tomizawa et al., 2000; Kagabu et al., 2005; Tian et al., 2007; Peter & Ralf, 2008). We report here crystal structure of one of these compounds, C₁₃H₁₉N₅O₄, the title compound (I). In the structure of (I) (Fig. 1), the triazine ring exhibits a half-chair conformation with a dihedral angle of 50.62° between plane A (C8, N3, C7, N2, C6) and plane B (C6, N1, C8). The bond angles C8–N1–C6, N1–C6–N2, C6–N2–C7, N2–C7–N3, C7–N3–C8 and N3–C8–N1 are 108.15 (19), 111.20 (18), 122.69 (19), 118.54 (19), 119.94 (18) and 111.98 (18)° respectively, in turn indicating asymmetry and strong tensility in the 1,3,5-hexahydrotriazine ring. The large discrepancy between the nitro O3–N5–N4 and O4–N5–N4 bond angles [116.1 (2) and 123.98 (19)° respectively] may be attributed to the intramolecular N2–H···O3 hydrogen bond (Table 1). There is also a single intermolecular N–H···O hydrogen bond associated with N2 (Fig. 2).

Interestingly, due to the transfer of the lone-pair of electrons from the hetero-N atoms to the C7═N4 double bond, the C7–N2 and C7–N3 bond lengths (1.327 (3) Å and 1.338 (3) Å), are both remarkably shorter than the pure C–N single bond (1.49 Å), but close to the C═C value (1.33 Å). The delocalization of the electrons extends as far as the electron-withdrawing nitro group, forming a coplanar π-electron network. A six-membered plane C (C7, N4, N5, O3, H2 and N2) is established by the intramolecular N2–H···O3 hydrogen bond. In addition, planes A and C form an enlarged plane D (comprising C6, C8, N3, C7, N2, H2, N4, O3 and O4).

Experimental

The title compound was prepared by the literature method (Zhu et al., 2010) and was recrystallized from ethanol-water (10:1), giving colorless crystals (yield 79.6%). ¹HNMR(CDCl₃, 400 Hz): 9.61 (1H, s, NH), 7.37–7.36 (2H, d, J = 0.8 Hz, furan—H), 6.38–6.34 (3H,m,furan—H), 4.49–4.47(6H, m, CH₂—furan, triazine–H), 3.97–3.85 (2H, m, CH₂—tetrahydrofuran), 3.53–3.12 (3H, m, tetrahydrofuran—H) 1.86–1.64(4H, m, tetrahydrofuran—H); IR(KBr, cm^-1) 3278(N—H), 1588 (C═N), 1195 (C—O—C), 1060 (C—N), Anal.: calcd. for C₁₃H₁₉N₅O₄: C 50.48, H 6.19, N 22.64%; found, C 51.03, H 6.17, N 22.75%.