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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2216.
Published online 2010 August 4. doi:  10.1107/S1600536810030266
PMCID: PMC3008036

(E)-1-(2,2-Dimeth­oxy­eth­yl)-2-(nitro­methyl­idene)imidazolidine

Abstract

In the title compound, C8H15N3O4, the 2-(nitro­methyl­ene)imidazolidine fragment is close to being planar (r.m.s. deviation = 0.027 Å), which may be correlated with delocalization of the electrons and the effect of the strongly electron-withdrawing NO2 group. An intra­molecular N—H(...)O link generates an S(6) ring. The same H atom also forms a weak inter­molecular N—H(...)O hydrogen bond, which results in C(7) chains propagating in [010].

Related literature

For background to neonicotinoid insecticides, see Moriya et al. (1992 [triangle]). For the synthesis, see: Tian et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2216-scheme1.jpg

Experimental

Crystal data

  • C8H15N3O4
  • M r = 217.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2216-efi1.jpg
  • a = 10.444 (2) Å
  • b = 6.8676 (17) Å
  • c = 14.441 (3) Å
  • β = 99.953 (14)°
  • V = 1020.2 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 296 K
  • 0.32 × 0.26 × 0.15 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.965, T max = 0.983
  • 8629 measured reflections
  • 2330 independent reflections
  • 1849 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.110
  • S = 1.06
  • 2330 reflections
  • 139 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030266/hb5567sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030266/hb5567Isup2.hkl

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20902037), the Opening Fund of Shanghai Key Laboratory of Chemical Biology (grant No. SKLCB-2008–08) and the Doctoral Foundation of the University of Jinan (B0542) for financial support.

supplementary crystallographic information

Comment

Since the debut of Imidacloprid in 1990s (Moriya et al., 1992), neonicotinoid insecticides have become rapidly an important chemical class of insecticides. Our interest was introducing oxygen atom into the lead struture and synthesizing a series of new compounds, in which the title compound (I) exhibited good insecticidal activities against pea aphids.

The structure of (I) is shown in Fig. 1 with the atom-numbering scheme. The delocalization of the electrons as far as the strong electron-withdrawing group, NO2, lead to a coplanar olefin-amine π-electron network. Intermolecular hydrogen bonds (N2—H2···O3) are found, and link the molecules into chains.

Experimental

The title compound was synthesized according to the literature (Tian et al., 2007). Colourless prisms of (I) were obtained by slow evaporation of the solution of dichloromethane and ethyl acetate of the title compound.

Refinement

H atoms bonded to N and O atoms were located in a difference map and refined with distance restraints of N—H = 0.87 (2) Å, and with Uiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically and refined using a riding model (including free rotation about the ethanol C—C bond), with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. The H atoms are shown as circles of arbitrary size.
Fig. 2.
Intermolecular hydrogen bonding in the crystal structure of (I).

Crystal data

C8H15N3O4F(000) = 464
Mr = 217.23Dx = 1.414 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3493 reflections
a = 10.444 (2) Åθ = 2.9–27.3°
b = 6.8676 (17) ŵ = 0.11 mm1
c = 14.441 (3) ÅT = 296 K
β = 99.953 (14)°Prism, colourless
V = 1020.2 (4) Å30.32 × 0.26 × 0.15 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer2330 independent reflections
Radiation source: fine-focus sealed tube1849 reflections with I > 2σ(I)
graphiteRint = 0.018
[var phi] and ω scansθmax = 27.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −13→13
Tmin = 0.965, Tmax = 0.983k = −8→8
8629 measured reflectionsl = −18→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.110w = 1/[σ2(Fo2) + (0.0508P)2 + 0.1844P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2330 reflectionsΔρmax = 0.25 e Å3
139 parametersΔρmin = −0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (2)

Special details

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)

xyzUiso*/Ueq
C10.00359 (12)0.08330 (19)0.63950 (8)0.0427 (3)
H1A0.05620.08600.59370.051*
C20.06233 (12)0.08637 (17)0.73529 (8)0.0406 (3)
C30.09094 (16)0.0794 (2)0.89827 (9)0.0563 (4)
H3A0.0816−0.03870.93330.068*
H3B0.07740.19130.93640.068*
C40.22254 (15)0.0880 (2)0.86762 (9)0.0597 (4)
H4A0.27010.20360.89210.072*
H4B0.2741−0.02620.88880.072*
C50.29097 (12)0.08628 (19)0.70666 (9)0.0461 (3)
H5A0.25330.03860.64470.055*
H5B0.3573−0.00570.73420.055*
C60.35394 (11)0.28135 (19)0.69663 (8)0.0414 (3)
H60.36430.34830.75740.050*
C70.31179 (18)0.5845 (2)0.62367 (12)0.0641 (4)
H7A0.33230.64100.68530.096*
H7B0.24460.65940.58600.096*
H7C0.38800.58460.59480.096*
C80.48007 (15)0.1666 (3)0.58408 (11)0.0699 (5)
H8A0.44950.03540.58730.105*
H8B0.56760.16500.57190.105*
H8C0.42520.23490.53430.105*
N1−0.12619 (11)0.07657 (17)0.61267 (8)0.0481 (3)
N20.00157 (12)0.0812 (2)0.80881 (8)0.0569 (3)
H2−0.08160.07920.80410.068*
N30.19059 (11)0.09392 (17)0.76437 (7)0.0473 (3)
O1−0.17315 (10)0.07294 (17)0.52580 (7)0.0654 (3)
O2−0.20198 (10)0.0741 (2)0.67215 (8)0.0725 (4)
O30.26831 (8)0.39078 (13)0.63099 (6)0.0476 (3)
O40.47709 (8)0.26264 (15)0.67127 (6)0.0524 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0413 (6)0.0489 (7)0.0367 (6)−0.0019 (5)0.0030 (5)0.0045 (5)
C20.0448 (6)0.0371 (6)0.0384 (6)−0.0040 (5)0.0029 (5)0.0046 (5)
C30.0749 (10)0.0563 (9)0.0359 (6)−0.0084 (7)0.0049 (6)0.0040 (6)
C40.0647 (9)0.0703 (10)0.0380 (7)−0.0080 (7)−0.0082 (6)0.0071 (6)
C50.0418 (6)0.0450 (7)0.0487 (7)−0.0006 (5)0.0001 (5)−0.0001 (5)
C60.0349 (6)0.0491 (7)0.0379 (6)−0.0021 (5)−0.0001 (4)−0.0028 (5)
C70.0774 (11)0.0510 (9)0.0627 (9)−0.0060 (7)0.0084 (8)0.0084 (7)
C80.0467 (8)0.1033 (13)0.0602 (9)0.0017 (8)0.0108 (7)−0.0211 (9)
N10.0461 (6)0.0522 (7)0.0437 (6)−0.0003 (5)0.0008 (5)0.0042 (5)
N20.0519 (6)0.0807 (9)0.0379 (6)−0.0050 (6)0.0073 (5)0.0037 (6)
N30.0450 (6)0.0570 (7)0.0368 (5)−0.0083 (5)−0.0013 (4)0.0060 (5)
O10.0562 (6)0.0879 (8)0.0445 (5)0.0038 (5)−0.0124 (4)0.0015 (5)
O20.0446 (6)0.1143 (11)0.0590 (6)−0.0025 (6)0.0096 (5)0.0061 (6)
O30.0438 (5)0.0477 (5)0.0479 (5)−0.0010 (4)−0.0014 (4)0.0026 (4)
O40.0342 (5)0.0713 (7)0.0495 (5)−0.0050 (4)0.0010 (4)−0.0086 (5)

Geometric parameters (Å, °)

C1—N11.3447 (17)C5—H5B0.9700
C1—C21.4131 (17)C6—O41.4028 (15)
C1—H1A0.9300C6—O31.4036 (15)
C2—N21.3282 (17)C6—H60.9800
C2—N31.3339 (16)C7—O31.4159 (18)
C3—N21.4573 (17)C7—H7A0.9600
C3—C41.516 (2)C7—H7B0.9600
C3—H3A0.9700C7—H7C0.9600
C3—H3B0.9700C8—O41.4265 (18)
C4—N31.4711 (17)C8—H8A0.9600
C4—H4A0.9700C8—H8B0.9600
C4—H4B0.9700C8—H8C0.9600
C5—N31.4485 (18)N1—O21.2647 (15)
C5—C61.5104 (18)N1—O11.2658 (14)
C5—H5A0.9700N2—H20.8600
N1—C1—C2121.87 (12)O4—C6—H6108.2
N1—C1—H1A119.1O3—C6—H6108.2
C2—C1—H1A119.1C5—C6—H6108.2
N2—C2—N3110.00 (11)O3—C7—H7A109.5
N2—C2—C1126.55 (12)O3—C7—H7B109.5
N3—C2—C1123.45 (12)H7A—C7—H7B109.5
N2—C3—C4102.41 (11)O3—C7—H7C109.5
N2—C3—H3A111.3H7A—C7—H7C109.5
C4—C3—H3A111.3H7B—C7—H7C109.5
N2—C3—H3B111.3O4—C8—H8A109.5
C4—C3—H3B111.3O4—C8—H8B109.5
H3A—C3—H3B109.2H8A—C8—H8B109.5
N3—C4—C3103.81 (11)O4—C8—H8C109.5
N3—C4—H4A111.0H8A—C8—H8C109.5
C3—C4—H4A111.0H8B—C8—H8C109.5
N3—C4—H4B111.0O2—N1—O1119.47 (11)
C3—C4—H4B111.0O2—N1—C1121.53 (11)
H4A—C4—H4B109.0O1—N1—C1119.00 (12)
N3—C5—C6113.17 (11)C2—N2—C3112.80 (12)
N3—C5—H5A108.9C2—N2—H2123.6
C6—C5—H5A108.9C3—N2—H2123.6
N3—C5—H5B108.9C2—N3—C5127.22 (11)
C6—C5—H5B108.9C2—N3—C4110.95 (11)
H5A—C5—H5B107.8C5—N3—C4121.47 (11)
O4—C6—O3112.25 (10)C6—O3—C7112.24 (10)
O4—C6—C5112.21 (11)C6—O4—C8115.70 (10)
O3—C6—C5107.61 (9)
N1—C1—C2—N20.7 (2)C1—C2—N3—C5−4.8 (2)
N1—C1—C2—N3−179.68 (12)N2—C2—N3—C41.74 (15)
N2—C3—C4—N30.09 (15)C1—C2—N3—C4−177.89 (12)
N3—C5—C6—O4158.56 (10)C6—C5—N3—C2105.58 (14)
N3—C5—C6—O3−77.48 (13)C6—C5—N3—C4−81.94 (15)
C2—C1—N1—O20.51 (19)C3—C4—N3—C2−1.09 (15)
C2—C1—N1—O1−179.59 (12)C3—C4—N3—C5−174.68 (12)
N3—C2—N2—C3−1.71 (16)O4—C6—O3—C7−62.38 (14)
C1—C2—N2—C3177.90 (12)C5—C6—O3—C7173.69 (12)
C4—C3—N2—C20.95 (16)O3—C6—O4—C8−61.01 (16)
N2—C2—N3—C5174.88 (12)C5—C6—O4—C860.33 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O20.862.092.6394 (17)121
N2—H2···O3i0.862.643.3554 (16)141

Symmetry codes: (i) −x, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5567).

References

  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Burla, M. C., Polidori, G., Camalli, M. & Spagna, R. (1999). SIR97 Universities of Bari, Perugia and Rome, Italy.
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Moriya, K., Shibuya, K., Hattori, Y., Tsuboi, S., Shiokawa, K. & Kagabu, S. (1992). Biosci. Biotech. Biochem.56, 364–365.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tian, Z. Z., Shao, X. S., Li, Z., Qian, X. H. & Huang, Q. C. (2007). J. Agric. Food Chem.55, 2288–2292. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography