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

Wang, G.; Li, D.; Li, H.

doi:10.1107/S1600536810039280

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2759

https://doi.org/10.1107/S1600536810039280

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

Gaolei Wang,^a Dongmei Li ^a ^* and He Li ^a

^aShandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, School of Chemistry and Chemical Engineering, University of Jinan, People's Republic of China
^*Correspondence e-mail: chm_lidm@ujn.edu.cn

(Received 26 September 2010; accepted 1 October 2010; online 9 October 2010)

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 ); Li et al. (2010 ). For background to neonicotinoid insecticides, see: Ohno et al. (2009 ); Jeschke & Nauen (2008 ).

Experimental

Crystal data

C₆H₁₁N₃O₃
M_r = 173.18
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.038
wR(F²) = 0.108
S = 1.11
1539 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.86	2.37	3.0463 (16)	136
N2—H2⋯O2	0.86	2.12	2.6600 (16)	121
O1—H1⋯O3ⁱⁱ	0.82	2.06	2.8814 (16)	175
Symmetry codes: (i) -x, -y+1, -z+2; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810039280/gk2305sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039280/gk2305Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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.

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

Crystal data top

C₆H₁₁N₃O₃	F(000) = 368
M_r = 173.18	D_x = 1.478 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yn	Cell parameters from 2585 reflections
a = 6.9422 (2) Å	θ = 3.2–28.8°
b = 8.7142 (3) Å	µ = 0.12 mm⁻¹
c = 12.9698 (4) Å	T = 293 K
β = 94.153 (3)°	Prism, colourless
V = 782.55 (4) Å³	0.31 × 0.29 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1539 independent reflections
Radiation source: fine-focus sealed tube	1186 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
Detector resolution: 16.0355 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→10
T_min = 0.967, T_max = 1.0	l = −15→15
4832 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0606P)² + 0.045P] where P = (F_o² + 2F_c²)/3
1539 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₆H₁₁N₃O₃	V = 782.55 (4) Å³
M_r = 173.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9422 (2) Å	µ = 0.12 mm⁻¹
b = 8.7142 (3) Å	T = 293 K
c = 12.9698 (4) Å	0.31 × 0.29 × 0.25 mm
β = 94.153 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1539 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1186 reflections with I > 2σ(I)
T_min = 0.967, T_max = 1.0	R_int = 0.017
4832 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.11	Δρ_max = 0.17 e Å⁻³
1539 reflections	Δρ_min = −0.17 e Å⁻³
110 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.7352 (2)	0.66673 (18)	0.73309 (13)	0.0428 (4)
H1A	0.7010	0.7696	0.7099	0.051*
H1B	0.8709	0.6509	0.7230	0.051*
C2	0.70406 (19)	0.65267 (18)	0.84644 (12)	0.0387 (4)
H2A	0.7338	0.5485	0.8687	0.046*
H2B	0.7932	0.7207	0.8851	0.046*
C3	0.4516 (2)	0.84632 (17)	0.89333 (14)	0.0481 (4)
H3A	0.4536	0.9106	0.8324	0.058*
H3B	0.5364	0.8904	0.9483	0.058*
C4	0.2490 (3)	0.82924 (18)	0.92650 (15)	0.0519 (5)
H4A	0.1570	0.8840	0.8802	0.062*
H4B	0.2396	0.8668	0.9964	0.062*
C5	0.36609 (19)	0.59107 (16)	0.88760 (10)	0.0296 (3)
C6	0.3790 (2)	0.43186 (17)	0.87112 (11)	0.0358 (4)
H6	0.4933	0.3920	0.8490	0.043*
N1	0.50847 (16)	0.68944 (13)	0.87087 (9)	0.0336 (3)
N2	0.21646 (17)	0.66554 (14)	0.92072 (10)	0.0403 (3)
H2	0.1119	0.6216	0.9370	0.048*
N3	0.23318 (18)	0.33545 (14)	0.88605 (10)	0.0371 (3)
O1	0.62388 (16)	0.55935 (12)	0.67291 (8)	0.0481 (3)
H1	0.5161	0.5949	0.6580	0.072*
O2	0.07390 (15)	0.38210 (13)	0.91700 (9)	0.0480 (3)
O3	0.25342 (18)	0.19348 (13)	0.86750 (10)	0.0580 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0326 (8)	0.0405 (9)	0.0571 (10)	−0.0014 (6)	0.0154 (7)	0.0017 (7)
C2	0.0258 (7)	0.0403 (9)	0.0499 (9)	−0.0013 (6)	0.0021 (6)	−0.0009 (7)
C3	0.0482 (10)	0.0322 (9)	0.0651 (11)	−0.0019 (7)	0.0120 (8)	−0.0064 (7)
C4	0.0552 (11)	0.0338 (9)	0.0689 (12)	0.0060 (7)	0.0210 (9)	−0.0038 (7)
C5	0.0292 (7)	0.0324 (8)	0.0274 (7)	0.0016 (6)	0.0026 (5)	0.0012 (5)
C6	0.0303 (8)	0.0324 (8)	0.0454 (8)	0.0010 (6)	0.0077 (6)	−0.0015 (6)
N1	0.0319 (6)	0.0298 (7)	0.0399 (7)	−0.0019 (5)	0.0087 (5)	−0.0032 (5)
N2	0.0329 (7)	0.0329 (7)	0.0568 (8)	0.0031 (5)	0.0162 (6)	−0.0007 (5)
N3	0.0389 (7)	0.0323 (7)	0.0400 (7)	−0.0019 (5)	0.0023 (5)	−0.0002 (5)
O1	0.0507 (7)	0.0442 (7)	0.0502 (7)	0.0038 (5)	0.0083 (5)	−0.0071 (5)
O2	0.0372 (6)	0.0480 (7)	0.0606 (7)	−0.0060 (5)	0.0163 (5)	−0.0029 (5)
O3	0.0593 (8)	0.0293 (7)	0.0858 (9)	−0.0038 (5)	0.0090 (7)	−0.0056 (6)

Geometric parameters (Å, º) top

C1—H1A	0.9700	C5—C6	1.408 (2)
C1—H1B	0.9700	C6—H6	0.9300
C1—C2	1.506 (2)	N1—C2	1.4523 (17)
C2—H2A	0.9700	N1—C3	1.4582 (19)
C2—H2B	0.9700	N2—H2	0.8600
C3—H3A	0.9700	N2—C4	1.445 (2)
C3—H3B	0.9700	N3—O3	1.2701 (16)
C3—C4	1.508 (2)	N3—C6	1.3406 (18)
C4—H4B	0.9700	O1—H1	0.8200
C4—H4A	0.9700	O1—C1	1.4123 (19)
C5—N1	1.3379 (17)	O2—N3	1.2702 (15)
C5—N2	1.3227 (17)

C1—O1—H1	109.5	N1—C5—C6	123.43 (13)
C1—C2—H2A	108.9	N1—C2—C1	113.42 (12)
C1—C2—H2B	108.9	N1—C2—H2A	108.9
H1A—C1—H1B	107.9	N1—C2—H2B	108.9
C2—N1—C3	121.44 (12)	N1—C3—H3A	111.0
C2—C1—H1A	109.2	N1—C3—H3B	111.0
C2—C1—H1B	109.2	N1—C3—C4	103.67 (12)
H2A—C2—H2B	107.7	N2—C5—N1	110.19 (12)
C3—C4—H4B	111.1	N2—C5—C6	126.39 (13)
C3—C4—H4A	111.1	N2—C4—C3	103.18 (12)
H3A—C3—H3B	109.0	N2—C4—H4B	111.1
C4—N2—H2	123.9	N2—C4—H4A	111.1
C4—C3—H3A	111.0	N3—C6—C5	122.59 (13)
C4—C3—H3B	111.0	N3—C6—H6	118.7
H4B—C4—H4A	109.1	O1—C1—H1A	109.2
C5—N1—C2	127.40 (12)	O1—C1—H1B	109.2
C5—N1—C3	110.75 (12)	O1—C1—C2	111.96 (12)
C5—N2—H2	123.9	O2—N3—C6	121.94 (12)
C5—N2—C4	112.19 (12)	O3—N3—O2	118.84 (12)
C5—C6—H6	118.7	O3—N3—C6	119.21 (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—C5	178.47 (14)	C5—N1—C2—C1	100.19 (16)
N1—C5—N2—C4	1.41 (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—N2	0.97 (18)	C6—C5—N1—C2	−8.2 (2)
N2—C5—N1—C2	171.93 (13)	C6—C5—N1—C3	179.16 (14)
N2—C5—N1—C3	−0.69 (16)	C6—C5—N2—C4	−178.44 (14)
N2—C5—C6—N3	1.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.37	3.0463 (16)	136
N2—H2···O2	0.86	2.12	2.6600 (16)	121
O1—H1···O3ⁱⁱ	0.82	2.06	2.8814 (16)	175

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

Experimental details

Crystal data
Chemical formula	C₆H₁₁N₃O₃
M_r	173.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.9422 (2), 8.7142 (3), 12.9698 (4)
β (°)	94.153 (3)
V (Å³)	782.55 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.31 × 0.29 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.967, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	4832, 1539, 1186
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.108, 1.11
No. of reflections	1539
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	2.37	3.0463 (16)	136
N2—H2···O2	0.86	2.12	2.6600 (16)	121
O1—H1···O3ⁱⁱ	0.82	2.06	2.8814 (16)	175

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

Acknowledgements

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.

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. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Jeschke, P. & Nauen, R. (2008). Pest. Manag. Sci. 64, 1084–1098. Web of Science CrossRef PubMed CAS Google Scholar
Li, D., Tian, Z., Wang, G., Wei, P. & Zhang, Y. (2010). Acta Cryst. E66, o2216. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ohno, I., Tomizawa, M., Durkin, K. A., Naruse, Y., Casida, J. E. & Kagabu, S. (2009). Chem. Res. Toxicol. 22, 476–482. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tian, Z., Dong, H., Li, D. & Wang, G. (2010). Acta Cryst. E66, o2330. Web of Science CSD CrossRef IUCr Journals Google Scholar