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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2517.
Published online 2009 September 26. doi:  10.1107/S1600536809037660
PMCID: PMC2970492

1-[(6-Chloro-3-pyrid­yl)meth­yl]-5-eth­oxy-8-nitro-1,2,3,5,6,7-hexa­hydro­imidazo[1,2-a]pyridine

Abstract

In the title compound, C15H19ClN4O3, an active agrochemical possessing insecticidal activity, the dihedral angle between the mean planes passing through the pyridine ring and the five-membered ring is 87.3 (2)°. The fused pyridine ring adopts a twisted sofa conformation. The mol­ecular structure features close intra­molecular C—H(...)N and C—H(...)O hydrogen bonding.

Related literature

For related literature, see: Kagabu et al. (2002 [triangle]); Moriya et al. (1992 [triangle]); Tian et al. (2007 [triangle]); Tokumitsu (1990 [triangle]).

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Object name is e-65-o2517-scheme1.jpg

Experimental

Crystal data

  • C15H19ClN4O3
  • M r = 338.79
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2517-efi1.jpg
  • a = 17.021 (3) Å
  • b = 5.5737 (8) Å
  • c = 18.334 (3) Å
  • β = 112.097 (3)°
  • V = 1611.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 290 K
  • 0.50 × 0.24 × 0.12 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.922, T max = 0.969
  • 8970 measured reflections
  • 3486 independent reflections
  • 1870 reflections with I > 2σ(I)
  • R int = 0.082

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.135
  • S = 0.82
  • 3486 reflections
  • 210 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037660/bx2230sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037660/bx2230Isup2.hkl

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

Acknowledgments

The authors thank the Opening Fund of Shanghai Key Laboratory of Chemical Biology (grant No. SKLCB-2008-08) and the Doctoral Foundation of the University of Jinan (grant No. XBS0823, B0542) for financial support.

supplementary crystallographic information

Comment

Since the debut of Imidacloprid in the 1990 decade (Moriya et al., 1992), neonicotinoid insecticides have become rapidly an important chemical class of insecticides. Nitromethylene compounds (Kagabu et al., 2002) exhibited remarkably higher biological activity but poor photostability compared with Imidacloprid. Our synthetic interest was introducing dicyclic ring into the lead structure to improve its photostability and synthesizing a series of new compounds, in which compound (I) exhibited good insecticidal activities against pea aphids and was slightly weaker than that of imidacloprid (Tian et al., 2007).The dihedral angle between the mean planes passing through the pyridine ring and the five membered ring is 87.3 (2)°. The six membered N2/C3/C4/C5/C6/C7 ring adopts a twist sofa conformation. The title compound C15H19ClN4O3 , is an active agrochemical possessing insecticidal activity. The dihedral angle between the mean planes passing through the pyridine ring and the five membered ring is 87.3 (2)°. The six membered N2/C3/C4/C5/C6/C7 ring adopts a twist sofa conformation.The molecular structure is stabilized by intramolecular C— H··· N and C— H··· O hydrogen bond, Table 1.

Experimental

The synthesis of the title compoud was following the reported method by Tokumitsu, 1990. Single crystals suitable for X-ray analysis were obtained by slow evaporation of the solution of dichloromethane and petroleum ether of the title compound. m.p. 399.8–400.8 K.

Refinement

H atoms were positioned geometrically and included in the refinement in the riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C) for pyridine H atoms, C—H = 0.97 Å and Uiso(H) = 1.2 Ueq(C) for the methylene H atoms, C—H = 0.96 Å and Uiso(H) = 1.5 Ueq(C) for the methyl H atoms, C—H = 0.98 Å and Uiso(H) = 1.2 Ueq(C) for the methenyl H atoms

Figures

Fig. 1.
The molecular structure of (a) with atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The H atoms are shown as circles of arbitrary size and intramolecular hydrogen bonds are indicated by dotted lines.

Crystal data

C15H19ClN4O3F(000) = 712
Mr = 338.79Dx = 1.396 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1727 reflections
a = 17.021 (3) Åθ = 4.8–47.4°
b = 5.5737 (8) ŵ = 0.26 mm1
c = 18.334 (3) ÅT = 290 K
β = 112.097 (3)°Prismatic, colourless
V = 1611.6 (4) Å30.50 × 0.24 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3486 independent reflections
Radiation source: fine-focus sealed tube1870 reflections with I > 2σ(I)
graphiteRint = 0.082
[var phi] and ω scansθmax = 27.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −21→21
Tmin = 0.922, Tmax = 0.969k = −7→7
8970 measured reflectionsl = −23→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.135w = 1/[σ2(Fo2) + (0.069P)2] where P = (Fo2 + 2Fc2)/3
S = 0.82(Δ/σ)max = 0.044
3486 reflectionsΔρmax = 0.32 e Å3
210 parametersΔρmin = −0.24 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: 0.020 (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
Cl1.20916 (4)0.34129 (13)0.43476 (5)0.0742 (3)
O10.58663 (11)0.9036 (4)0.35790 (10)0.0669 (5)
O20.69588 (12)0.4707 (4)0.16844 (11)0.0739 (6)
O30.81680 (12)0.5033 (3)0.26680 (11)0.0653 (5)
N10.84352 (11)0.9213 (3)0.35853 (10)0.0428 (5)
N20.71934 (11)1.0384 (4)0.35902 (11)0.0484 (5)
N30.74299 (13)0.5777 (4)0.22900 (12)0.0517 (5)
N41.05820 (12)0.4680 (4)0.42526 (12)0.0542 (5)
C10.86309 (14)1.0659 (5)0.43064 (14)0.0528 (6)
H1A0.90761.18140.43610.063*
H1B0.88060.96450.47700.063*
C20.77991 (15)1.1909 (5)0.41832 (15)0.0594 (7)
H2A0.76871.19460.46640.071*
H2B0.77931.35330.39910.071*
C30.75815 (13)0.9028 (4)0.32102 (13)0.0406 (5)
C40.71043 (14)0.7723 (4)0.25471 (13)0.0451 (6)
C50.61813 (14)0.8220 (5)0.21354 (14)0.0582 (7)
H5A0.58570.69210.22360.070*
H5B0.60450.82930.15720.070*
C60.59349 (15)1.0563 (5)0.24097 (15)0.0602 (7)
H6A0.53221.06890.22100.072*
H6B0.61501.18900.21970.072*
C70.62807 (15)1.0737 (5)0.32935 (15)0.0552 (7)
H70.61611.23400.34450.066*
C80.59553 (18)0.9382 (6)0.43754 (16)0.0753 (9)
H8A0.57321.09410.44330.090*
H8B0.65510.93340.47150.090*
C90.5492 (2)0.7483 (7)0.46073 (19)0.1023 (12)
H9A0.48960.76200.42990.123*
H9B0.55870.76520.51550.123*
H9C0.56910.59400.45190.123*
C110.89956 (13)0.9436 (4)0.31525 (13)0.0455 (6)
H11A0.91311.11180.31300.055*
H11B0.86950.88910.26170.055*
C120.98050 (13)0.8050 (4)0.35017 (12)0.0393 (5)
C130.98935 (14)0.6091 (4)0.39838 (13)0.0490 (6)
H130.94430.57190.41340.059*
C141.12093 (14)0.5302 (4)0.40378 (13)0.0454 (6)
C151.12235 (14)0.7269 (4)0.35956 (13)0.0465 (6)
H151.16990.76510.34860.056*
C161.05008 (14)0.8655 (4)0.33212 (13)0.0462 (6)
H161.04801.00000.30140.055*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl0.0596 (4)0.0681 (5)0.0967 (6)0.0181 (3)0.0313 (4)0.0041 (4)
O10.0668 (11)0.0879 (15)0.0610 (12)−0.0114 (10)0.0413 (10)−0.0097 (10)
O20.0778 (12)0.0823 (14)0.0702 (13)−0.0259 (11)0.0374 (11)−0.0376 (11)
O30.0691 (12)0.0575 (12)0.0737 (13)0.0125 (9)0.0320 (10)−0.0075 (9)
N10.0411 (11)0.0494 (12)0.0425 (11)−0.0023 (8)0.0210 (9)−0.0026 (9)
N20.0439 (11)0.0575 (13)0.0477 (12)0.0013 (9)0.0216 (9)−0.0130 (10)
N30.0583 (13)0.0558 (13)0.0503 (13)−0.0090 (11)0.0311 (11)−0.0095 (11)
N40.0553 (12)0.0513 (13)0.0624 (14)0.0059 (10)0.0293 (11)0.0106 (10)
C10.0529 (14)0.0594 (16)0.0473 (14)−0.0102 (12)0.0201 (12)−0.0093 (12)
C20.0641 (16)0.0623 (18)0.0556 (16)−0.0076 (13)0.0269 (13)−0.0186 (13)
C30.0447 (13)0.0413 (13)0.0407 (13)0.0016 (10)0.0216 (11)0.0027 (10)
C40.0475 (13)0.0493 (15)0.0436 (14)−0.0033 (11)0.0231 (11)−0.0055 (11)
C50.0476 (14)0.081 (2)0.0484 (15)−0.0038 (13)0.0204 (12)−0.0060 (13)
C60.0466 (14)0.082 (2)0.0545 (16)0.0109 (13)0.0218 (12)0.0084 (14)
C70.0500 (14)0.0604 (17)0.0626 (17)0.0079 (12)0.0297 (13)−0.0033 (13)
C80.0739 (19)0.104 (3)0.0543 (18)0.0098 (17)0.0314 (15)0.0030 (17)
C90.111 (3)0.143 (3)0.071 (2)−0.020 (2)0.055 (2)0.006 (2)
C110.0480 (13)0.0474 (14)0.0479 (14)−0.0009 (11)0.0257 (11)0.0059 (11)
C120.0426 (12)0.0410 (13)0.0379 (12)−0.0033 (10)0.0193 (10)−0.0017 (10)
C130.0483 (14)0.0533 (16)0.0545 (15)−0.0001 (11)0.0299 (12)0.0080 (12)
C140.0433 (13)0.0477 (15)0.0453 (14)0.0016 (11)0.0167 (11)−0.0066 (11)
C150.0435 (13)0.0538 (15)0.0494 (14)−0.0068 (11)0.0257 (11)−0.0048 (12)
C160.0488 (14)0.0493 (14)0.0451 (14)−0.0073 (11)0.0230 (11)0.0045 (11)

Geometric parameters (Å, °)

Cl—C141.745 (2)C5—H5A0.9700
O1—C71.396 (3)C5—H5B0.9700
O1—C81.423 (3)C6—C71.505 (4)
O2—N31.250 (2)C6—H6A0.9700
O3—N31.255 (2)C6—H6B0.9700
N1—C31.358 (3)C7—H70.9800
N1—C111.458 (3)C8—C91.475 (4)
N1—C11.475 (3)C8—H8A0.9700
N2—C31.356 (3)C8—H8B0.9700
N2—C71.453 (3)C9—H9A0.9600
N2—C21.457 (3)C9—H9B0.9600
N3—C41.379 (3)C9—H9C0.9600
N4—C141.316 (3)C11—C121.497 (3)
N4—C131.342 (3)C11—H11A0.9700
C1—C21.517 (3)C11—H11B0.9700
C1—H1A0.9700C12—C131.377 (3)
C1—H1B0.9700C12—C161.386 (3)
C2—H2A0.9700C13—H130.9300
C2—H2B0.9700C14—C151.369 (3)
C3—C41.387 (3)C15—C161.378 (3)
C4—C51.491 (3)C15—H150.9300
C5—C61.514 (4)C16—H160.9300
C7—O1—C8114.8 (2)H6A—C6—H6B108.0
C3—N1—C11121.70 (18)O1—C7—N2112.8 (2)
C3—N1—C1109.47 (18)O1—C7—C6108.2 (2)
C11—N1—C1117.89 (18)N2—C7—C6108.9 (2)
C3—N2—C7122.79 (19)O1—C7—H7108.9
C3—N2—C2111.33 (18)N2—C7—H7108.9
C7—N2—C2123.86 (19)C6—C7—H7108.9
O2—N3—O3120.5 (2)O1—C8—C9109.7 (3)
O2—N3—C4118.2 (2)O1—C8—H8A109.7
O3—N3—C4121.2 (2)C9—C8—H8A109.7
C14—N4—C13115.5 (2)O1—C8—H8B109.7
N1—C1—C2103.53 (17)C9—C8—H8B109.7
N1—C1—H1A111.1H8A—C8—H8B108.2
C2—C1—H1A111.1C8—C9—H9A109.5
N1—C1—H1B111.1C8—C9—H9B109.5
C2—C1—H1B111.1H9A—C9—H9B109.5
H1A—C1—H1B109.0C8—C9—H9C109.5
N2—C2—C1101.66 (19)H9A—C9—H9C109.5
N2—C2—H2A111.4H9B—C9—H9C109.5
C1—C2—H2A111.4N1—C11—C12114.11 (18)
N2—C2—H2B111.4N1—C11—H11A108.7
C1—C2—H2B111.4C12—C11—H11A108.7
H2A—C2—H2B109.3N1—C11—H11B108.7
N2—C3—N1109.43 (19)C12—C11—H11B108.7
N2—C3—C4120.32 (19)H11A—C11—H11B107.6
N1—C3—C4130.3 (2)C13—C12—C16116.7 (2)
N3—C4—C3122.3 (2)C13—C12—C11123.00 (19)
N3—C4—C5117.1 (2)C16—C12—C11120.3 (2)
C3—C4—C5120.3 (2)N4—C13—C12124.8 (2)
C4—C5—C6111.3 (2)N4—C13—H13117.6
C4—C5—H5A109.4C12—C13—H13117.6
C6—C5—H5A109.4N4—C14—C15125.8 (2)
C4—C5—H5B109.4N4—C14—Cl116.08 (18)
C6—C5—H5B109.4C15—C14—Cl118.11 (18)
H5A—C5—H5B108.0C14—C15—C16117.0 (2)
C5—C6—C7111.6 (2)C14—C15—H15121.5
C5—C6—H6A109.3C16—C15—H15121.5
C7—C6—H6A109.3C15—C16—C12120.1 (2)
C5—C6—H6B109.3C15—C16—H16119.9
C7—C6—H6B109.3C12—C16—H16119.9
C3—N1—C1—C2−16.3 (3)C8—O1—C7—N275.1 (3)
C11—N1—C1—C2128.5 (2)C8—O1—C7—C6−164.3 (2)
C3—N2—C2—C1−19.3 (3)C3—N2—C7—O191.2 (3)
C7—N2—C2—C1176.5 (2)C2—N2—C7—O1−106.4 (3)
N1—C1—C2—N220.5 (2)C3—N2—C7—C6−28.9 (3)
C7—N2—C3—N1174.3 (2)C2—N2—C7—C6133.5 (2)
C2—N2—C3—N19.9 (3)C5—C6—C7—O1−67.8 (3)
C7—N2—C3—C4−6.0 (3)C5—C6—C7—N255.2 (3)
C2—N2—C3—C4−170.4 (2)C7—O1—C8—C9180.0 (2)
C11—N1—C3—N2−138.6 (2)C3—N1—C11—C12−140.6 (2)
C1—N1—C3—N24.7 (3)C1—N1—C11—C1279.0 (2)
C11—N1—C3—C441.7 (4)N1—C11—C12—C1323.2 (3)
C1—N1—C3—C4−175.0 (2)N1—C11—C12—C16−159.4 (2)
O2—N3—C4—C3−179.6 (2)C14—N4—C13—C121.3 (3)
O3—N3—C4—C33.1 (3)C16—C12—C13—N4−3.6 (3)
O2—N3—C4—C57.1 (3)C11—C12—C13—N4173.9 (2)
O3—N3—C4—C5−170.2 (2)C13—N4—C14—C152.3 (3)
N2—C3—C4—N3−158.8 (2)C13—N4—C14—Cl−177.37 (17)
N1—C3—C4—N320.8 (4)N4—C14—C15—C16−3.2 (3)
N2—C3—C4—C514.3 (3)Cl—C14—C15—C16176.44 (17)
N1—C3—C4—C5−166.1 (2)C14—C15—C16—C120.6 (3)
N3—C4—C5—C6−173.1 (2)C13—C12—C16—C152.4 (3)
C3—C4—C5—C613.5 (3)C11—C12—C16—C15−175.1 (2)
C4—C5—C6—C7−48.2 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11B···O30.972.352.803 (3)108
C13—H13···N10.932.542.891 (3)103

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2230).

References

  • Bruker (1997). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Kagabu, S., Nishiwaki, H., Sato, K., Hibi, M., Yamaoka, N. & Nakagawa, Y. (2002). Pest. Manag. Sci.58, 483–490. [PubMed]
  • Moriya, K., Shibuya, K., Hattori, Y., Tsuboi, S., Shiokawa, K. & Kagabu, S. (1992). Biosci. Biotechnol. 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]
  • Tokumitsu, T. (1990). Bull. Chem. Soc. Jpn, 63, 1921–1924.

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