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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2759.
Published online 2010 October 9. doi:  10.1107/S1600536810039280
PMCID: PMC3009051

2-[(E)-2-(Nitro­methyl­idene)imidazolidin-1-yl]ethanol

Abstract

In the title compound, C6H11N3O3, the imidazolidine NH group is involved in a three-center N—H(...)O hydrogen bond, with intra­molecular and inter­molecular branches, to the nitro group O atoms. The centrosymmetric dimers that are formed are further connected by O—H(...)O hydrogen bonds between the hy­droxy and nitro groups into a two-dimensional polymeric structure extending parallel to (101).

Related literature

For related structures, see: Tian et al. (2010 [triangle]); Li et al. (2010 [triangle]). For background to neonicotinoid insecticides, see: Ohno et al. (2009 [triangle]); Jeschke & Nauen (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2759-scheme1.jpg

Experimental

Crystal data

  • C6H11N3O3
  • M r = 173.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2759-efi1.jpg
  • a = 6.9422 (2) Å
  • b = 8.7142 (3) Å
  • c = 12.9698 (4) Å
  • β = 94.153 (3)°
  • V = 782.55 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 K
  • 0.31 × 0.29 × 0.25 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.967, T max = 1.0
  • 4832 measured reflections
  • 1539 independent reflections
  • 1186 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.108
  • S = 1.11
  • 1539 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.17 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/S1600536810039280/gk2305sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039280/gk2305Isup2.hkl

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20902037) and the Doctoral Foundation of University of Jinan (B0542) for financial support.

supplementary crystallographic information

Comment

Compared with conventional insecticides, nicotinoid insecticides have rapidly grown and become an important chemical class of insecticides in recent years because of their novel structure and mode of action (Ohno et al., 2009 and Jeschke et al., 2008). Here, we have synthesized a new compound by introducing an oxygen atom into the lead struture instead of nitrogen atom.

The structure of the title compound is shown in Fig. 1 with the atom-numbering scheme. The title compound is homolog of (E)-1-(2,2-dimethoxyethyl)-2-(nitromethylene)imidazolidine (Li et al., 2010). The imidazolidine ring is close to planar (r.m.s. deviation = 0.006 Å). Intramolecular H-bonding of N–H···O type exists and completes an S(6) ring motif. The packing of the molecules is stabilized by N–H···O and O–H···O hydrogen bonds and van der Waal's forces.

Experimental

A solution of 2-(2-aminoethylamino)ethanol (2 mmol), and 1,1-bis(thiomethyl)-2-nitroethylene (2 mmol) in 30 ml of ethanol was refluxed for 8 h and then cooled to room temperature. Evaporation under reduced pressure gave the title product after purifiction by flash chromatography. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of dichloromethane and ethyl acetate of the title compound.

Refinement

All H atoms were placed in their calculated positions and then refined using riding model with C—H = 0.93–0.97 Å, O—H = 0.82 Å , N—H = 0.86 Å and Uiso(H) = 1.2 Ueq(C,N) or Uiso(H) = 1.5 Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with atom numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. The H atoms are shown as spheres of arbitrary size.
Fig. 2.
Inter- and intramolecular hydrogen bonding in the titlecrystal structure.

Crystal data

C6H11N3O3F(000) = 368
Mr = 173.18Dx = 1.478 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ynCell parameters from 2585 reflections
a = 6.9422 (2) Åθ = 3.2–28.8°
b = 8.7142 (3) ŵ = 0.12 mm1
c = 12.9698 (4) ÅT = 293 K
β = 94.153 (3)°Prism, colourless
V = 782.55 (4) Å30.31 × 0.29 × 0.25 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer1539 independent reflections
Radiation source: fine-focus sealed tube1186 reflections with I > 2σ(I)
graphiteRint = 0.017
Detector resolution: 16.0355 pixels mm-1θmax = 26.0°, θmin = 3.2°
ω scansh = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −10→10
Tmin = 0.967, Tmax = 1.0l = −15→15
4832 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.0606P)2 + 0.045P] where P = (Fo2 + 2Fc2)/3
1539 reflections(Δ/σ)max < 0.001
110 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = −0.17 e Å3

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
C10.7352 (2)0.66673 (18)0.73309 (13)0.0428 (4)
H1A0.70100.76960.70990.051*
H1B0.87090.65090.72300.051*
C20.70406 (19)0.65267 (18)0.84644 (12)0.0387 (4)
H2A0.73380.54850.86870.046*
H2B0.79320.72070.88510.046*
C30.4516 (2)0.84632 (17)0.89333 (14)0.0481 (4)
H3A0.45360.91060.83240.058*
H3B0.53640.89040.94830.058*
C40.2490 (3)0.82924 (18)0.92650 (15)0.0519 (5)
H4A0.15700.88400.88020.062*
H4B0.23960.86680.99640.062*
C50.36609 (19)0.59107 (16)0.88760 (10)0.0296 (3)
C60.3790 (2)0.43186 (17)0.87112 (11)0.0358 (4)
H60.49330.39200.84900.043*
N10.50847 (16)0.68944 (13)0.87087 (9)0.0336 (3)
N20.21646 (17)0.66554 (14)0.92072 (10)0.0403 (3)
H20.11190.62160.93700.048*
N30.23318 (18)0.33545 (14)0.88605 (10)0.0371 (3)
O10.62388 (16)0.55935 (12)0.67291 (8)0.0481 (3)
H10.51610.59490.65800.072*
O20.07390 (15)0.38210 (13)0.91700 (9)0.0480 (3)
O30.25342 (18)0.19348 (13)0.86750 (10)0.0580 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0326 (8)0.0405 (9)0.0571 (10)−0.0014 (6)0.0154 (7)0.0017 (7)
C20.0258 (7)0.0403 (9)0.0499 (9)−0.0013 (6)0.0021 (6)−0.0009 (7)
C30.0482 (10)0.0322 (9)0.0651 (11)−0.0019 (7)0.0120 (8)−0.0064 (7)
C40.0552 (11)0.0338 (9)0.0689 (12)0.0060 (7)0.0210 (9)−0.0038 (7)
C50.0292 (7)0.0324 (8)0.0274 (7)0.0016 (6)0.0026 (5)0.0012 (5)
C60.0303 (8)0.0324 (8)0.0454 (8)0.0010 (6)0.0077 (6)−0.0015 (6)
N10.0319 (6)0.0298 (7)0.0399 (7)−0.0019 (5)0.0087 (5)−0.0032 (5)
N20.0329 (7)0.0329 (7)0.0568 (8)0.0031 (5)0.0162 (6)−0.0007 (5)
N30.0389 (7)0.0323 (7)0.0400 (7)−0.0019 (5)0.0023 (5)−0.0002 (5)
O10.0507 (7)0.0442 (7)0.0502 (7)0.0038 (5)0.0083 (5)−0.0071 (5)
O20.0372 (6)0.0480 (7)0.0606 (7)−0.0060 (5)0.0163 (5)−0.0029 (5)
O30.0593 (8)0.0293 (7)0.0858 (9)−0.0038 (5)0.0090 (7)−0.0056 (6)

Geometric parameters (Å, °)

C1—H1A0.9700C5—C61.408 (2)
C1—H1B0.9700C6—H60.9300
C1—C21.506 (2)N1—C21.4523 (17)
C2—H2A0.9700N1—C31.4582 (19)
C2—H2B0.9700N2—H20.8600
C3—H3A0.9700N2—C41.445 (2)
C3—H3B0.9700N3—O31.2701 (16)
C3—C41.508 (2)N3—C61.3406 (18)
C4—H4B0.9700O1—H10.8200
C4—H4A0.9700O1—C11.4123 (19)
C5—N11.3379 (17)O2—N31.2702 (15)
C5—N21.3227 (17)
C1—O1—H1109.5N1—C5—C6123.43 (13)
C1—C2—H2A108.9N1—C2—C1113.42 (12)
C1—C2—H2B108.9N1—C2—H2A108.9
H1A—C1—H1B107.9N1—C2—H2B108.9
C2—N1—C3121.44 (12)N1—C3—H3A111.0
C2—C1—H1A109.2N1—C3—H3B111.0
C2—C1—H1B109.2N1—C3—C4103.67 (12)
H2A—C2—H2B107.7N2—C5—N1110.19 (12)
C3—C4—H4B111.1N2—C5—C6126.39 (13)
C3—C4—H4A111.1N2—C4—C3103.18 (12)
H3A—C3—H3B109.0N2—C4—H4B111.1
C4—N2—H2123.9N2—C4—H4A111.1
C4—C3—H3A111.0N3—C6—C5122.59 (13)
C4—C3—H3B111.0N3—C6—H6118.7
H4B—C4—H4A109.1O1—C1—H1A109.2
C5—N1—C2127.40 (12)O1—C1—H1B109.2
C5—N1—C3110.75 (12)O1—C1—C2111.96 (12)
C5—N2—H2123.9O2—N3—C6121.94 (12)
C5—N2—C4112.19 (12)O3—N3—O2118.84 (12)
C5—C6—H6118.7O3—N3—C6119.21 (13)
O1—C1—C2—N1−64.63 (17)C2—N1—C3—C4−173.37 (14)
O2—N3—C6—C5−0.6 (2)C3—N1—C2—C1−87.91 (16)
O3—N3—C6—C5178.47 (14)C5—N1—C2—C1100.19 (16)
N1—C5—N2—C41.41 (17)C5—N1—C3—C4−0.24 (17)
N1—C5—C6—N3−178.43 (12)C5—N2—C4—C3−1.48 (19)
N1—C3—C4—N20.97 (18)C6—C5—N1—C2−8.2 (2)
N2—C5—N1—C2171.93 (13)C6—C5—N1—C3179.16 (14)
N2—C5—N1—C3−0.69 (16)C6—C5—N2—C4−178.44 (14)
N2—C5—C6—N31.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.862.373.0463 (16)136
N2—H2···O20.862.122.6600 (16)121
O1—H1···O3ii0.822.062.8814 (16)175

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2305).

References

  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Bruker (2005). APEX2, SAINTandSADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Jeschke, P. & Nauen, R. (2008). Pest. Manag. Sci.64, 1084–1098. [PubMed]
  • Li, D., Tian, Z., Wang, G., Wei, P. & Zhang, Y. (2010). Acta Cryst. E66, o2216. [PMC free article] [PubMed]
  • Ohno, I., Tomizawa, M., Durkin, K. A., Naruse, Y., Casida, J. E. & Kagabu, S. (2009). Chem. Res. Toxicol.22, 476–482. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tian, Z., Dong, H., Li, D. & Wang, G. (2010). Acta Cryst. E66, o2330. [PMC free article] [PubMed]

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