(E)-N-(6-Chloro-3-pyridylmeth­yl)-N-ethyl-N′-methyl-2-nitro­ethyl­ene-1,1-diamine

Xu, L.-Z.; Yang, Z.; Yi, X.; An, G.-W.

doi:10.1107/S1600536808013317

organic compounds

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Volume 64| Part 6| June 2008| Page o1074

doi:10.1107/S1600536808013317

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(E)-N-(6-Chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitroethylene-1,1-diamine

Liang-Zhong Xu,^a ^* Zhi Yang,^a Xu Yi ^a and Guang-Wei An ^a

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: qknhs@yahoo.com.cn

(Received 23 April 2008; accepted 6 May 2008; online 14 May 2008)

In the title compound, C₁₁H₁₅ClN₄O₂, the amino group is involved in intra- and intermolecular N—H⋯O hydrogen bonds. The former contributes to the molecular conformation, while the latter link the molecules into centrosymmetric dimers. The crystal structure also exhibits weak intermolecular C—H⋯O interactions.

Related literature

For the properties of neonicotinoid insecticides, see: Wang et al. (2001 ); Isao et al. (1993 ). For related crystal structures, see: Jiang et al. (2007 ); Xia et al. (2007 ).

Experimental

Crystal data

C₁₁H₁₅ClN₄O₂
M_r = 270.72
Monoclinic, P 2₁ /n
a = 7.7252 (15) Å
b = 7.9281 (16) Å
c = 20.787 (4) Å
β = 92.34 (3)°
V = 1272.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 113 (2) K
0.14 × 0.12 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.959, T_max = 0.988
7120 measured reflections
2238 independent reflections
1970 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.089
S = 1.05
2238 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.86	2.12	2.6376 (16)	118
N3—H3A⋯O1ⁱ	0.86	2.38	3.0778 (17)	138
C6—H6A⋯O1ⁱⁱ	0.97	2.58	3.508 (2)	160
C3—H3⋯O2ⁱⁱⁱ	0.93	2.50	3.1101 (19)	123
Symmetry codes: (i) -x+1, -y+2, -z; (ii) -x, -y+2, -z; (iii) x, y-1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013317/cv2407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013317/cv2407Isup2.hkl

checkCIF report

Comment top

Nitenpyram is a new chloro-nicotine type insecticide (Wang et al., 2001) possessing a wide spectum of useful properties (Isao et al., 1993). We report here the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are in agreement with those reported for the related structures (Jiang et al., 2007; Xia et al., 2007). The pyridine ring and plane N2/N3/C9/C11 form a dihedral angle of 48.8 (2)°. The amino group is involved in intra- and intermolecular N-H···O hydrogen bonds (Table 1). The intermolecular N-H···O hydrogen bonds link the molecules into centrosymmetric dimers. The crystal packing exhibits also weak intermolecular C—H···O interactions (Table 1).

Related literature top

For the properties of neonicotinoid insecticides, see: Wang et al. (2001); Isao et al. (1993). For related crystal structures, see: Jiang et al. (2007); Xia et al. (2007).

Experimental top

A solution comprising N-((6-chloropyridin-3-yl)methyl)ethanamine(0.1 mol) in trichloromethane(30 ml) was slowly added from a dropping-funnel to a mixture of 1,1,1-trichloro-2-nitro-ethane(0.15 mol), trichloromethane(30 ml) and an aqueous solution of sodium carbonate(40%, 53 g) in a flask equipped with stirrer and reflux condenser. After the mixture was stirred for 1 h while maintaining the temperature at 273–280k, an aqueous solution of methylamine(30%, 30 g) was then added dropwise, followed by a two hours stirring at room temperature. The reaction mixture were extracted with trichloromethane, the title compound (16.2 g, yield 60%) could be afforded after ethyl oxide was added to the concentration remnants on cooling. The single-crystal suitable for X-ray measurements was obtained by recrystallization from trichloromethane-ethyl acetate(1:1) at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.

(E)-N-(6-Chloro-3-pyridylmethyl)-N-ethyl-N'-methyl-2-nitroethylene-1,1-diamine top

Crystal data top

C₁₁H₁₅ClN₄O₂	F(000) = 568
M_r = 270.72	D_x = 1.414 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3653 reflections
a = 7.7252 (15) Å	θ = 2.0–27.9°
b = 7.9281 (16) Å	µ = 0.30 mm⁻¹
c = 20.787 (4) Å	T = 113 K
β = 92.34 (3)°	Block, yellow
V = 1272.0 (4) Å³	0.14 × 0.12 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2238 independent reflections
Radiation source: rotating anode	1970 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.031
ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −9→5
T_min = 0.959, T_max = 0.988	k = −8→9
7120 measured reflections	l = −24→23

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.053P)² + 0.2942P] where P = (F_o² + 2F_c²)/3
2238 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₁H₁₅ClN₄O₂	V = 1272.0 (4) Å³
M_r = 270.72	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.7252 (15) Å	µ = 0.30 mm⁻¹
b = 7.9281 (16) Å	T = 113 K
c = 20.787 (4) Å	0.14 × 0.12 × 0.04 mm
β = 92.34 (3)°

Data collection top

Rigaku Saturn diffractometer	2238 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1970 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.988	R_int = 0.031
7120 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.05	Δρ_max = 0.33 e Å⁻³
2238 reflections	Δρ_min = −0.34 e Å⁻³
165 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
Cl1	−0.46834 (6)	0.13093 (5)	0.15973 (2)	0.03277 (16)
O1	0.31814 (14)	1.08651 (13)	−0.00180 (6)	0.0256 (3)
O2	0.11880 (15)	1.26510 (13)	0.02461 (6)	0.0297 (3)
N1	−0.37165 (16)	0.43140 (16)	0.19759 (6)	0.0218 (3)
N2	0.10858 (15)	0.74385 (14)	0.12607 (6)	0.0154 (3)
N3	0.34655 (15)	0.80473 (14)	0.06527 (6)	0.0164 (3)
H3A	0.4171	0.8837	0.0555	0.020*
N4	0.19059 (16)	1.12460 (14)	0.03211 (6)	0.0187 (3)
C1	−0.34845 (19)	0.31625 (19)	0.15333 (7)	0.0194 (3)
C2	−0.23838 (19)	0.33022 (19)	0.10271 (8)	0.0193 (3)
H2	−0.2261	0.2429	0.0734	0.023*
C3	−0.14779 (18)	0.47891 (18)	0.09762 (7)	0.0183 (3)
H3	−0.0727	0.4941	0.0642	0.022*
C4	−0.16921 (18)	0.60648 (17)	0.14276 (7)	0.0157 (3)
C5	−0.28034 (19)	0.57502 (19)	0.19164 (7)	0.0193 (3)
H5	−0.2931	0.6584	0.2225	0.023*
C6	−0.07572 (18)	0.77266 (17)	0.13772 (7)	0.0170 (3)
H6A	−0.1280	0.8384	0.1027	0.020*
H6B	−0.0863	0.8360	0.1773	0.020*
C7	0.20362 (19)	0.64947 (18)	0.17777 (7)	0.0177 (3)
H7A	0.2889	0.5772	0.1586	0.021*
H7B	0.1228	0.5777	0.1996	0.021*
C8	0.2939 (2)	0.7633 (2)	0.22653 (9)	0.0301 (4)
H8A	0.3829	0.8259	0.2062	0.045*
H8B	0.3449	0.6965	0.2608	0.045*
H8C	0.2115	0.8402	0.2436	0.045*
C9	0.19636 (18)	0.85310 (17)	0.08850 (7)	0.0142 (3)
C10	0.4040 (2)	0.63299 (18)	0.05466 (8)	0.0206 (3)
H10A	0.4731	0.5955	0.0913	0.031*
H10B	0.4718	0.6292	0.0170	0.031*
H10C	0.3050	0.5607	0.0486	0.031*
C11	0.12900 (18)	1.01529 (17)	0.07620 (7)	0.0169 (3)
H11	0.0359	1.0503	0.0999	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0374 (3)	0.0288 (2)	0.0319 (3)	−0.01993 (18)	0.00009 (19)	0.00218 (17)
O1	0.0213 (6)	0.0257 (6)	0.0307 (7)	0.0037 (5)	0.0121 (5)	0.0098 (5)
O2	0.0367 (7)	0.0148 (5)	0.0384 (8)	0.0088 (5)	0.0118 (6)	0.0096 (5)
N1	0.0195 (6)	0.0264 (7)	0.0195 (7)	−0.0078 (6)	0.0008 (5)	0.0030 (6)
N2	0.0126 (6)	0.0143 (6)	0.0191 (7)	0.0006 (5)	0.0006 (5)	0.0041 (5)
N3	0.0137 (6)	0.0119 (6)	0.0241 (7)	−0.0011 (5)	0.0041 (5)	0.0007 (5)
N4	0.0191 (7)	0.0145 (6)	0.0226 (7)	0.0014 (5)	0.0033 (5)	0.0023 (5)
C1	0.0171 (7)	0.0202 (7)	0.0203 (8)	−0.0049 (6)	−0.0052 (6)	0.0054 (6)
C2	0.0197 (7)	0.0172 (7)	0.0208 (8)	0.0025 (6)	−0.0012 (6)	0.0005 (6)
C3	0.0149 (7)	0.0202 (8)	0.0199 (8)	0.0017 (6)	0.0028 (6)	0.0032 (6)
C4	0.0115 (7)	0.0170 (7)	0.0183 (8)	0.0018 (6)	−0.0023 (6)	0.0040 (6)
C5	0.0179 (7)	0.0218 (7)	0.0181 (8)	−0.0025 (6)	0.0003 (6)	−0.0006 (6)
C6	0.0147 (7)	0.0154 (7)	0.0211 (8)	0.0012 (6)	0.0033 (6)	0.0022 (6)
C7	0.0171 (7)	0.0176 (7)	0.0183 (8)	0.0002 (6)	−0.0006 (6)	0.0053 (6)
C8	0.0348 (9)	0.0279 (9)	0.0267 (10)	−0.0077 (7)	−0.0094 (7)	0.0053 (7)
C9	0.0141 (7)	0.0134 (7)	0.0148 (8)	−0.0016 (6)	−0.0018 (6)	−0.0010 (5)
C10	0.0200 (8)	0.0165 (7)	0.0252 (9)	0.0052 (6)	0.0026 (7)	−0.0012 (6)
C11	0.0163 (7)	0.0150 (7)	0.0197 (8)	0.0005 (6)	0.0056 (6)	0.0008 (6)

Geometric parameters (Å, º) top

Cl1—C1	1.7447 (15)	C4—C5	1.379 (2)
O1—N4	1.2711 (16)	C4—C6	1.508 (2)
O2—N4	1.2512 (16)	C5—H5	0.9300
N1—C1	1.314 (2)	C6—H6A	0.9700
N1—C5	1.3478 (19)	C6—H6B	0.9700
N2—C9	1.3650 (18)	C7—C8	1.507 (2)
N2—C6	1.4717 (17)	C7—H7A	0.9700
N2—C7	1.4796 (19)	C7—H7B	0.9700
N3—C9	1.3313 (18)	C8—H8A	0.9600
N3—C10	1.4517 (18)	C8—H8B	0.9600
N3—H3A	0.8600	C8—H8C	0.9600
N4—C11	1.3613 (18)	C9—C11	1.4066 (19)
C1—C2	1.384 (2)	C10—H10A	0.9600
C2—C3	1.377 (2)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.394 (2)	C11—H11	0.9300
C3—H3	0.9300

C1—N1—C5	115.85 (13)	N2—C6—H6B	109.6
C9—N2—C6	120.14 (12)	C4—C6—H6B	109.6
C9—N2—C7	119.54 (12)	H6A—C6—H6B	108.1
C6—N2—C7	114.44 (11)	N2—C7—C8	112.82 (12)
C9—N3—C10	126.98 (12)	N2—C7—H7A	109.0
C9—N3—H3A	116.5	C8—C7—H7A	109.0
C10—N3—H3A	116.5	N2—C7—H7B	109.0
O2—N4—O1	119.49 (12)	C8—C7—H7B	109.0
O2—N4—C11	119.03 (12)	H7A—C7—H7B	107.8
O1—N4—C11	121.48 (12)	C7—C8—H8A	109.5
N1—C1—C2	125.63 (13)	C7—C8—H8B	109.5
N1—C1—Cl1	116.35 (11)	H8A—C8—H8B	109.5
C2—C1—Cl1	118.03 (12)	C7—C8—H8C	109.5
C3—C2—C1	117.18 (14)	H8A—C8—H8C	109.5
C3—C2—H2	121.4	H8B—C8—H8C	109.5
C1—C2—H2	121.4	N3—C9—N2	119.04 (12)
C2—C3—C4	119.65 (14)	N3—C9—C11	121.26 (13)
C2—C3—H3	120.2	N2—C9—C11	119.69 (12)
C4—C3—H3	120.2	N3—C10—H10A	109.5
C5—C4—C3	117.33 (13)	N3—C10—H10B	109.5
C5—C4—C6	121.56 (13)	H10A—C10—H10B	109.5
C3—C4—C6	121.10 (13)	N3—C10—H10C	109.5
N1—C5—C4	124.34 (14)	H10A—C10—H10C	109.5
N1—C5—H5	117.8	H10B—C10—H10C	109.5
C4—C5—H5	117.8	N4—C11—C9	124.57 (13)
N2—C6—C4	110.19 (11)	N4—C11—H11	117.7
N2—C6—H6A	109.6	C9—C11—H11	117.7
C4—C6—H6A	109.6

C5—N1—C1—C2	0.8 (2)	C3—C4—C6—N2	−47.41 (19)
C5—N1—C1—Cl1	−179.06 (11)	C9—N2—C7—C8	58.95 (17)
N1—C1—C2—C3	−1.3 (2)	C6—N2—C7—C8	−94.11 (15)
Cl1—C1—C2—C3	178.57 (11)	C10—N3—C9—N2	23.9 (2)
C1—C2—C3—C4	0.3 (2)	C10—N3—C9—C11	−157.47 (15)
C2—C3—C4—C5	1.0 (2)	C6—N2—C9—N3	−163.24 (13)
C2—C3—C4—C6	−178.39 (13)	C7—N2—C9—N3	45.24 (19)
C1—N1—C5—C4	0.7 (2)	C6—N2—C9—C11	18.2 (2)
C3—C4—C5—N1	−1.6 (2)	C7—N2—C9—C11	−133.36 (14)
C6—C4—C5—N1	177.82 (13)	O2—N4—C11—C9	179.01 (14)
C9—N2—C6—C4	145.80 (13)	O1—N4—C11—C9	−0.4 (2)
C7—N2—C6—C4	−61.31 (16)	N3—C9—C11—N4	11.8 (2)
C5—C4—C6—N2	133.23 (14)	N2—C9—C11—N4	−169.61 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.12	2.6376 (16)	118
N3—H3A···O1ⁱ	0.86	2.38	3.0778 (17)	138
C6—H6A···O1ⁱⁱ	0.97	2.58	3.508 (2)	160
C3—H3···O2ⁱⁱⁱ	0.93	2.50	3.1101 (19)	123

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅ClN₄O₂
M_r	270.72
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	7.7252 (15), 7.9281 (16), 20.787 (4)
β (°)	92.34 (3)
V (Å³)	1272.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.14 × 0.12 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.959, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7120, 2238, 1970
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.089, 1.05
No. of reflections	2238
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.34

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.12	2.6376 (16)	117.8
N3—H3A···O1ⁱ	0.86	2.38	3.0778 (17)	138.4
C6—H6A···O1ⁱⁱ	0.97	2.58	3.508 (2)	160.0
C3—H3···O2ⁱⁱⁱ	0.93	2.50	3.1101 (19)	123.1

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

References

Isao, M., Koichi, I. & Takanori, T. (1993). J. Pesticide Sci. 18, 41–48. Google Scholar
Jiang, H., Yu, C.-X., Tu, S.-J., Wang, X.-S. & Yao, C.-S. (2007). Acta Cryst. E63, o298–o299. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, J. J., Han, Z. J. & Wang, Y. C. (2001). Zhiwu Baohu Xuebao, 28, 178–182. CAS Google Scholar
Xia, Y., Ding, X.-L., Ge, Y.-Q., Liu, L.-D. & Zhao, B.-X. (2007). Acta Cryst. E63, o394–o395. Web of Science CSD CrossRef IUCr Journals Google Scholar

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(E)-N-(6-Chloro-3-pyridylmeth­yl)-N-ethyl-N′-methyl-2-nitro­ethyl­ene-1,1-di­amine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

(E)-N-(6-Chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitroethylene-1,1-diamine