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

Li, D.; Tian, Z.; Wang, G.; Wei, P.; Zhang, Y.

doi:10.1107/S1600536810030266

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2216

https://doi.org/10.1107/S1600536810030266

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

Dongmei Li,^a Zhongzhen Tian,^a ^* Gaolei Wang,^a Peifeng Wei ^a and Yanming Zhang ^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_tianzz@ujn.edu.cn

(Received 21 July 2010; accepted 29 July 2010; online 4 August 2010)

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 ). For the synthesis, see: Tian et al. (2007 ).

Experimental

Crystal data

C₈H₁₅N₃O₄
M_r = 217.23
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.110
S = 1.06
2330 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2	0.86	2.09	2.6394 (17)	121
N2—H2⋯O3ⁱ	0.86	2.64	3.3554 (16)	141
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536810030266/hb5567sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030266/hb5567Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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

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 (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).

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

Crystal data top

C₈H₁₅N₃O₄	F(000) = 464
M_r = 217.23	D_x = 1.414 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3493 reflections
a = 10.444 (2) Å	θ = 2.9–27.3°
b = 6.8676 (17) Å	µ = 0.11 mm⁻¹
c = 14.441 (3) Å	T = 296 K
β = 99.953 (14)°	Prism, colourless
V = 1020.2 (4) Å³	0.32 × 0.26 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2330 independent reflections
Radiation source: fine-focus sealed tube	1849 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
φ and ω scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
T_min = 0.965, T_max = 0.983	k = −8→8
8629 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0508P)² + 0.1844P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2330 reflections	Δρ_max = 0.25 e Å⁻³
139 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

Crystal data top

C₈H₁₅N₃O₄	V = 1020.2 (4) Å³
M_r = 217.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.444 (2) Å	µ = 0.11 mm⁻¹
b = 6.8676 (17) Å	T = 296 K
c = 14.441 (3) Å	0.32 × 0.26 × 0.15 mm
β = 99.953 (14)°

Data collection top

Bruker APEXII CCD diffractometer	2330 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1849 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.983	R_int = 0.018
8629 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.06	Δρ_max = 0.25 e Å⁻³
2330 reflections	Δρ_min = −0.16 e Å⁻³
139 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	0.00359 (12)	0.08330 (19)	0.63950 (8)	0.0427 (3)
H1A	0.0562	0.0860	0.5937	0.051*
C2	0.06233 (12)	0.08637 (17)	0.73529 (8)	0.0406 (3)
C3	0.09094 (16)	0.0794 (2)	0.89827 (9)	0.0563 (4)
H3A	0.0816	−0.0387	0.9333	0.068*
H3B	0.0774	0.1913	0.9364	0.068*
C4	0.22254 (15)	0.0880 (2)	0.86762 (9)	0.0597 (4)
H4A	0.2701	0.2036	0.8921	0.072*
H4B	0.2741	−0.0262	0.8888	0.072*
C5	0.29097 (12)	0.08628 (19)	0.70666 (9)	0.0461 (3)
H5A	0.2533	0.0386	0.6447	0.055*
H5B	0.3573	−0.0057	0.7342	0.055*
C6	0.35394 (11)	0.28135 (19)	0.69663 (8)	0.0414 (3)
H6	0.3643	0.3483	0.7574	0.050*
C7	0.31179 (18)	0.5845 (2)	0.62367 (12)	0.0641 (4)
H7A	0.3323	0.6410	0.6853	0.096*
H7B	0.2446	0.6594	0.5860	0.096*
H7C	0.3880	0.5846	0.5948	0.096*
C8	0.48007 (15)	0.1666 (3)	0.58408 (11)	0.0699 (5)
H8A	0.4495	0.0354	0.5873	0.105*
H8B	0.5676	0.1650	0.5719	0.105*
H8C	0.4252	0.2349	0.5343	0.105*
N1	−0.12619 (11)	0.07657 (17)	0.61267 (8)	0.0481 (3)
N2	0.00157 (12)	0.0812 (2)	0.80881 (8)	0.0569 (3)
H2	−0.0816	0.0792	0.8041	0.068*
N3	0.19059 (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)
O3	0.26831 (8)	0.39078 (13)	0.63099 (6)	0.0476 (3)
O4	0.47709 (8)	0.26264 (15)	0.67127 (6)	0.0524 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0413 (6)	0.0489 (7)	0.0367 (6)	−0.0019 (5)	0.0030 (5)	0.0045 (5)
C2	0.0448 (6)	0.0371 (6)	0.0384 (6)	−0.0040 (5)	0.0029 (5)	0.0046 (5)
C3	0.0749 (10)	0.0563 (9)	0.0359 (6)	−0.0084 (7)	0.0049 (6)	0.0040 (6)
C4	0.0647 (9)	0.0703 (10)	0.0380 (7)	−0.0080 (7)	−0.0082 (6)	0.0071 (6)
C5	0.0418 (6)	0.0450 (7)	0.0487 (7)	−0.0006 (5)	0.0001 (5)	−0.0001 (5)
C6	0.0349 (6)	0.0491 (7)	0.0379 (6)	−0.0021 (5)	−0.0001 (4)	−0.0028 (5)
C7	0.0774 (11)	0.0510 (9)	0.0627 (9)	−0.0060 (7)	0.0084 (8)	0.0084 (7)
C8	0.0467 (8)	0.1033 (13)	0.0602 (9)	0.0017 (8)	0.0108 (7)	−0.0211 (9)
N1	0.0461 (6)	0.0522 (7)	0.0437 (6)	−0.0003 (5)	0.0008 (5)	0.0042 (5)
N2	0.0519 (6)	0.0807 (9)	0.0379 (6)	−0.0050 (6)	0.0073 (5)	0.0037 (6)
N3	0.0450 (6)	0.0570 (7)	0.0368 (5)	−0.0083 (5)	−0.0013 (4)	0.0060 (5)
O1	0.0562 (6)	0.0879 (8)	0.0445 (5)	0.0038 (5)	−0.0124 (4)	0.0015 (5)
O2	0.0446 (6)	0.1143 (11)	0.0590 (6)	−0.0025 (6)	0.0096 (5)	0.0061 (6)
O3	0.0438 (5)	0.0477 (5)	0.0479 (5)	−0.0010 (4)	−0.0014 (4)	0.0026 (4)
O4	0.0342 (5)	0.0713 (7)	0.0495 (5)	−0.0050 (4)	0.0010 (4)	−0.0086 (5)

Geometric parameters (Å, º) top

C1—N1	1.3447 (17)	C5—H5B	0.9700
C1—C2	1.4131 (17)	C6—O4	1.4028 (15)
C1—H1A	0.9300	C6—O3	1.4036 (15)
C2—N2	1.3282 (17)	C6—H6	0.9800
C2—N3	1.3339 (16)	C7—O3	1.4159 (18)
C3—N2	1.4573 (17)	C7—H7A	0.9600
C3—C4	1.516 (2)	C7—H7B	0.9600
C3—H3A	0.9700	C7—H7C	0.9600
C3—H3B	0.9700	C8—O4	1.4265 (18)
C4—N3	1.4711 (17)	C8—H8A	0.9600
C4—H4A	0.9700	C8—H8B	0.9600
C4—H4B	0.9700	C8—H8C	0.9600
C5—N3	1.4485 (18)	N1—O2	1.2647 (15)
C5—C6	1.5104 (18)	N1—O1	1.2658 (14)
C5—H5A	0.9700	N2—H2	0.8600

N1—C1—C2	121.87 (12)	O4—C6—H6	108.2
N1—C1—H1A	119.1	O3—C6—H6	108.2
C2—C1—H1A	119.1	C5—C6—H6	108.2
N2—C2—N3	110.00 (11)	O3—C7—H7A	109.5
N2—C2—C1	126.55 (12)	O3—C7—H7B	109.5
N3—C2—C1	123.45 (12)	H7A—C7—H7B	109.5
N2—C3—C4	102.41 (11)	O3—C7—H7C	109.5
N2—C3—H3A	111.3	H7A—C7—H7C	109.5
C4—C3—H3A	111.3	H7B—C7—H7C	109.5
N2—C3—H3B	111.3	O4—C8—H8A	109.5
C4—C3—H3B	111.3	O4—C8—H8B	109.5
H3A—C3—H3B	109.2	H8A—C8—H8B	109.5
N3—C4—C3	103.81 (11)	O4—C8—H8C	109.5
N3—C4—H4A	111.0	H8A—C8—H8C	109.5
C3—C4—H4A	111.0	H8B—C8—H8C	109.5
N3—C4—H4B	111.0	O2—N1—O1	119.47 (11)
C3—C4—H4B	111.0	O2—N1—C1	121.53 (11)
H4A—C4—H4B	109.0	O1—N1—C1	119.00 (12)
N3—C5—C6	113.17 (11)	C2—N2—C3	112.80 (12)
N3—C5—H5A	108.9	C2—N2—H2	123.6
C6—C5—H5A	108.9	C3—N2—H2	123.6
N3—C5—H5B	108.9	C2—N3—C5	127.22 (11)
C6—C5—H5B	108.9	C2—N3—C4	110.95 (11)
H5A—C5—H5B	107.8	C5—N3—C4	121.47 (11)
O4—C6—O3	112.25 (10)	C6—O3—C7	112.24 (10)
O4—C6—C5	112.21 (11)	C6—O4—C8	115.70 (10)
O3—C6—C5	107.61 (9)

N1—C1—C2—N2	0.7 (2)	C1—C2—N3—C5	−4.8 (2)
N1—C1—C2—N3	−179.68 (12)	N2—C2—N3—C4	1.74 (15)
N2—C3—C4—N3	0.09 (15)	C1—C2—N3—C4	−177.89 (12)
N3—C5—C6—O4	158.56 (10)	C6—C5—N3—C2	105.58 (14)
N3—C5—C6—O3	−77.48 (13)	C6—C5—N3—C4	−81.94 (15)
C2—C1—N1—O2	0.51 (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—C3	177.90 (12)	C5—C6—O3—C7	173.69 (12)
C4—C3—N2—C2	0.95 (16)	O3—C6—O4—C8	−61.01 (16)
N2—C2—N3—C5	174.88 (12)	C5—C6—O4—C8	60.33 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	2.09	2.6394 (17)	121
N2—H2···O3ⁱ	0.86	2.64	3.3554 (16)	141

Symmetry code: (i) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₅N₃O₄
M_r	217.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.444 (2), 6.8676 (17), 14.441 (3)
β (°)	99.953 (14)
V (Å³)	1020.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.26 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.965, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	8629, 2330, 1849
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.110, 1.06
No. of reflections	2330
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16

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···O2	0.86	2.09	2.6394 (17)	121
N2—H2···O3ⁱ	0.86	2.64	3.3554 (16)	141

Symmetry code: (i) −x, y−1/2, −z+3/2.

Acknowledgements

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.

References

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