(E)-1-[(1,3-Dioxan-4-yl)meth­yl]-2-(nitro­methyl­idene)imidazolidine

Tian, Z.; Dong, H.; Li, D.; Wang, G.

doi:10.1107/S1600536810032691

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2359

https://doi.org/10.1107/S1600536810032691

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(E)-1-[(1,3-Dioxan-4-yl)methyl]-2-(nitromethylidene)imidazolidine

Zhongzhen Tian,^a Haijun Dong,^b Dongmei Li ^a ^* and Gaolei Wang ^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, and ^bSchool of Sciences, University of Jinan, People's Republic of China
^*Correspondence e-mail: chm_lidm@ujn.edu.cn

(Received 8 August 2010; accepted 14 August 2010; online 21 August 2010)

In the title compound, C₉H₁₅N₃O₄, the 1,3-dioxane ring displays a chair conformation and the five-membered ring is close to planar (r.m.s. deviation = 0.054 Å). An intramolecular N—H⋯O hydrogen bond to one of the nitro-group O atoms generates an S(6) ring. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into C(6) chains propagating in [010] and a C—H⋯O link also occurs.

Related literature

For a related structure, see Tian et al. (2009 ). For background to neonicotinoid insecticides, see Mori et al. (2001 ); Ohno et al. (2009 ); Jeschke & Nauen (2008 ); Kagabu (1997 ); Tian et al. (2007 ).

Experimental

Crystal data

C₉H₁₅N₃O₄
M_r = 229.24
Monoclinic, P 2₁ /n
a = 5.0138 (4) Å
b = 9.8092 (9) Å
c = 21.7162 (18) Å
V = 1068.03 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.42 × 0.26 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.954, T_max = 0.982
5866 measured reflections
1933 independent reflections
1395 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.174
S = 1.10
1933 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.28 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	2.17	2.694 (3)	119
N2—H2⋯O1ⁱ	0.86	2.17	2.824 (3)	133
C1—H1⋯O2ⁱⁱ	0.93	2.42	3.249 (3)	148
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536810032691/hb5607sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032691/hb5607Isup2.hkl

checkCIF report

Comment top

By virtue of novel modes of action (targeting insect nicotinic acetylcholine receptors (nAChRs) (Ohno et al., 2009), low mammalian toxicity, broad insecticidal spectra, and good systemic properties (Jeschke et al., 2008), neonicotinoids has accounted for 18% of world insecticide sales in the past decades. Our interest was introducing oxygen atoms into the lead struture and synthesizing a series of new compounds, in which the title compound exhibited moderate insecticidal activities against pea aphids.

The structure of the title compound is shown in Fig. 1 with the atom-numbering scheme. The 1,3-dioxane ring displays an chair conformation with bond angles lying between 110.0 (2)° and 111.7 (2)°. The nitro moiety is in trans configuration relative to the 1,3-dioxane ring and coplanar with the olefin-amine plane [N3—C2—C1—N1 = -177.49 (18)°]. Around N2 and N3 atoms the sums of the angles are 360° and 359.72°, respectively, indicating that they are typical sp² hybridized and leading to an essentially planar imidazole ring.

Related literature top

For a related structure, see Tian et al. (2009). For background to neonicotinoid insecticides, see Mori et al. (2001); Ohno et al. (2009); Jeschke et al. (2008); Kagabu (1997); Tian et al. (2007).

Experimental top

A solution of N-((1,3-dioxan-4-yl)methyl)ethane-1,2-diamine (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. Colourless prisms of (I) were obtained by slow evaporation of a solution of the title compound in dichloromethane and ethyl acetate.

Structure description top

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 40% probability level. The H atoms are shown as spheres of arbitrary size.

(E)-1-[(1,3-Dioxan-4-yl)methyl]-2-(nitromethylidene)imidazolidine top

Crystal data top

C₉H₁₅N₃O₄	F(000) = 488
M_r = 229.24	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2831 reflections
a = 5.0138 (4) Å	θ = 3.5–28.7°
b = 9.8092 (9) Å	µ = 0.11 mm⁻¹
c = 21.7162 (18) Å	T = 296 K
β = 90°	Prism, colourless
V = 1068.03 (16) Å³	0.42 × 0.26 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1933 independent reflections
Radiation source: fine-focus sealed tube	1395 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.4°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.954, T_max = 0.982	k = −11→11
5866 measured reflections	l = −26→26

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.1126P)²] where P = (F_o² + 2F_c²)/3
1933 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₉H₁₅N₃O₄	V = 1068.03 (16) Å³
M_r = 229.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.0138 (4) Å	µ = 0.11 mm⁻¹
b = 9.8092 (9) Å	T = 296 K
c = 21.7162 (18) Å	0.42 × 0.26 × 0.16 mm
β = 90°

Data collection top

Bruker APEXII CCD diffractometer	1933 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1395 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.982	R_int = 0.022
5866 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 1.10	Δρ_max = 0.35 e Å⁻³
1933 reflections	Δρ_min = −0.28 e Å⁻³
145 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
O2	0.7955 (3)	0.71286 (16)	0.23056 (8)	0.0532 (5)
N1	0.7422 (4)	0.58813 (19)	0.22961 (9)	0.0420 (5)
C2	0.3945 (4)	0.6124 (2)	0.30617 (10)	0.0343 (5)
O3	0.2691 (4)	0.39753 (16)	0.44986 (7)	0.0536 (5)
N2	0.4042 (4)	0.74655 (19)	0.31417 (9)	0.0435 (5)
H2	0.5038	0.8003	0.2930	0.052*
C1	0.5501 (4)	0.5344 (2)	0.26581 (10)	0.0390 (6)
H1	0.5196	0.4409	0.2638	0.047*
N3	0.2104 (4)	0.55718 (19)	0.34370 (8)	0.0421 (5)
O1	0.8720 (4)	0.51016 (18)	0.19406 (9)	0.0640 (6)
C5	0.1287 (5)	0.4153 (2)	0.34624 (11)	0.0432 (6)
H5A	0.1514	0.3753	0.3057	0.052*
H5B	−0.0597	0.4115	0.3563	0.052*
C6	0.2786 (5)	0.3314 (2)	0.39185 (10)	0.0406 (6)
H6	0.4653	0.3268	0.3787	0.049*
O4	0.2921 (5)	0.1954 (2)	0.50513 (9)	0.0741 (7)
C7	0.1743 (5)	0.1882 (2)	0.39737 (11)	0.0453 (6)
H7A	0.2109	0.1387	0.3596	0.054*
H7B	−0.0175	0.1904	0.4032	0.054*
C4	0.0734 (5)	0.6627 (3)	0.37948 (11)	0.0474 (6)
H4B	0.0835	0.6438	0.4233	0.057*
H4A	−0.1125	0.6699	0.3675	0.057*
C3	0.2257 (5)	0.7920 (2)	0.36326 (11)	0.0507 (7)
H3A	0.1061	0.8629	0.3488	0.061*
H3B	0.3255	0.8258	0.3984	0.061*
C9	0.4109 (7)	0.3220 (3)	0.49462 (13)	0.0653 (8)
H9A	0.5930	0.3086	0.4808	0.078*
H9B	0.4163	0.3731	0.5328	0.078*
C8	0.3037 (7)	0.1152 (3)	0.45115 (13)	0.0651 (8)
H8B	0.2132	0.0293	0.4583	0.078*
H8A	0.4885	0.0956	0.4413	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0554 (11)	0.0286 (10)	0.0756 (13)	−0.0030 (7)	0.0114 (9)	0.0037 (8)
N1	0.0450 (11)	0.0278 (11)	0.0533 (12)	0.0051 (8)	0.0010 (9)	0.0052 (9)
C2	0.0377 (11)	0.0255 (12)	0.0397 (12)	0.0020 (9)	−0.0111 (9)	0.0038 (9)
O3	0.0719 (11)	0.0445 (11)	0.0443 (10)	−0.0009 (9)	−0.0041 (8)	−0.0026 (8)
N2	0.0474 (11)	0.0262 (10)	0.0569 (12)	0.0006 (8)	0.0004 (9)	0.0001 (9)
C1	0.0458 (13)	0.0261 (12)	0.0451 (13)	−0.0020 (9)	−0.0025 (10)	0.0019 (10)
N3	0.0524 (12)	0.0317 (11)	0.0423 (11)	−0.0025 (8)	0.0010 (9)	0.0015 (8)
O1	0.0772 (13)	0.0398 (11)	0.0750 (13)	0.0116 (9)	0.0302 (10)	0.0017 (10)
C5	0.0450 (13)	0.0410 (14)	0.0437 (13)	−0.0091 (11)	−0.0063 (10)	0.0035 (10)
C6	0.0441 (12)	0.0376 (13)	0.0399 (12)	−0.0056 (10)	−0.0015 (9)	0.0002 (10)
O4	0.1233 (19)	0.0549 (12)	0.0441 (10)	−0.0022 (12)	0.0030 (11)	0.0089 (9)
C7	0.0536 (14)	0.0350 (13)	0.0471 (14)	−0.0038 (10)	0.0041 (11)	−0.0019 (10)
C4	0.0462 (13)	0.0482 (15)	0.0477 (13)	0.0052 (11)	−0.0027 (10)	−0.0031 (12)
C3	0.0677 (17)	0.0349 (14)	0.0494 (14)	0.0088 (12)	−0.0027 (12)	−0.0024 (11)
C9	0.095 (2)	0.0565 (18)	0.0446 (15)	0.0001 (15)	−0.0174 (14)	0.0038 (13)
C8	0.096 (2)	0.0411 (16)	0.0584 (17)	0.0051 (15)	0.0003 (15)	0.0049 (13)

Geometric parameters (Å, º) top

O2—N1	1.253 (2)	C6—H6	0.9800
N1—C1	1.350 (3)	C6—C7	1.504 (3)
N1—O1	1.267 (2)	O4—C9	1.396 (4)
C2—N2	1.329 (3)	O4—C8	1.413 (3)
C2—C1	1.401 (3)	C7—H7A	0.9700
C2—N3	1.345 (3)	C7—H7B	0.9700
O3—C6	1.418 (3)	C7—C8	1.516 (4)
O3—C9	1.414 (3)	C4—H4B	0.9700
N2—H2	0.8600	C4—H4A	0.9700
N2—C3	1.462 (3)	C4—C3	1.522 (4)
C1—H1	0.9300	C3—H3A	0.9700
N3—C5	1.452 (3)	C3—H3B	0.9700
N3—C4	1.465 (3)	C9—H9A	0.9700
C5—H5A	0.9700	C9—H9B	0.9700
C5—H5B	0.9700	C8—H8B	0.9700
C5—C6	1.491 (3)	C8—H8A	0.9700

O2—N1—C1	121.61 (19)	H5A—C5—H5B	107.6
O2—N1—O1	119.35 (19)	C6—C5—H5A	108.7
N1—C1—C2	123.2 (2)	C6—C5—H5B	108.7
N1—C1—H1	118.4	C6—C7—H7A	109.5
C2—N2—H2	124.0	C6—C7—H7B	109.5
C2—N2—C3	112.0 (2)	C6—C7—C8	110.7 (2)
C2—C1—H1	118.4	O4—C9—O3	111.3 (2)
C2—N3—C5	127.03 (19)	O4—C9—H9A	109.4
C2—N3—C4	111.03 (19)	O4—C9—H9B	109.4
O3—C6—C5	108.72 (19)	O4—C8—C7	111.0 (2)
O3—C6—H6	108.2	O4—C8—H8B	109.4
O3—C6—C7	110.17 (18)	O4—C8—H8A	109.4
O3—C9—H9A	109.4	C7—C6—H6	108.2
O3—C9—H9B	109.4	C7—C8—H8B	109.4
N2—C2—C1	127.1 (2)	C7—C8—H8A	109.4
N2—C2—N3	110.1 (2)	H7A—C7—H7B	108.1
N2—C3—C4	102.82 (18)	C4—C3—H3A	111.2
N2—C3—H3A	111.2	C4—C3—H3B	111.2
N2—C3—H3B	111.2	H4B—C4—H4A	109.1
N3—C2—C1	122.80 (19)	C3—N2—H2	124.0
N3—C5—H5A	108.7	C3—C4—H4B	111.1
N3—C5—H5B	108.7	C3—C4—H4A	111.1
N3—C5—C6	114.35 (18)	H3A—C3—H3B	109.1
N3—C4—H4B	111.1	C9—O3—C6	110.8 (2)
N3—C4—H4A	111.1	C9—O4—C8	110.0 (2)
N3—C4—C3	103.34 (19)	H9A—C9—H9B	108.0
O1—N1—C1	119.04 (19)	C8—C7—H7A	109.5
C5—N3—C4	121.66 (19)	C8—C7—H7B	109.5
C5—C6—H6	108.2	H8B—C8—H8A	108.0
C5—C6—C7	113.16 (18)

O2—N1—C1—C2	0.9 (3)	N3—C5—C6—O3	52.3 (3)
C2—N2—C3—C4	−7.0 (2)	N3—C5—C6—C7	175.06 (19)
C2—N3—C5—C6	92.4 (3)	N3—C4—C3—N2	7.6 (2)
C2—N3—C4—C3	−6.3 (2)	O1—N1—C1—C2	−179.4 (2)
O3—C6—C7—C8	−49.0 (3)	C5—N3—C4—C3	179.39 (19)
N2—C2—C1—N1	1.8 (3)	C5—C6—C7—C8	−170.9 (2)
N2—C2—N3—C5	176.06 (19)	C6—O3—C9—O4	−64.4 (3)
N2—C2—N3—C4	2.1 (2)	C6—C7—C8—O4	49.6 (3)
C1—C2—N2—C3	−176.0 (2)	C4—N3—C5—C6	−94.3 (3)
C1—C2—N3—C5	−4.5 (3)	C9—O3—C6—C5	−179.5 (2)
C1—C2—N3—C4	−178.49 (19)	C9—O3—C6—C7	56.0 (3)
N3—C2—N2—C3	3.4 (2)	C9—O4—C8—C7	−56.4 (3)
N3—C2—C1—N1	−177.49 (18)	C8—O4—C9—O3	64.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	2.17	2.694 (3)	119
N2—H2···O1ⁱ	0.86	2.17	2.824 (3)	133
C1—H1···O2ⁱⁱ	0.93	2.42	3.249 (3)	148

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

Experimental details

Crystal data
Chemical formula	C₉H₁₅N₃O₄
M_r	229.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.0138 (4), 9.8092 (9), 21.7162 (18)
β (°)	90, 90, 90
V (Å³)	1068.03 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.42 × 0.26 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.954, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5866, 1933, 1395
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.174, 1.10
No. of reflections	1933
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.28

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	2.17	2.694 (3)	119
N2—H2···O1ⁱ	0.86	2.17	2.824 (3)	133
C1—H1···O2ⁱⁱ	0.93	2.42	3.249 (3)	148

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

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 Doctoral Foundation of University of Jinan (B0542) for financial support.

References

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