Ethyl 2-{3-[(6-chloro-pyridin-3-yl)meth-yl]-2-(nitro-imino)-imidazolidin-1-yl}acetate.

In the title compound, C(13)H(16)ClN(5)O(4), the imidazole ring is in a slight envelope conformation. The dihedral angle between the pyridine ring and the four essentially planar atoms [maximum deviation 0.015 (2) Å] of the imidazole ring is 80.8 (1)°. In, the crystal, weak C-H⋯O and C-H⋯N hydrogen bonds are present. In addition, there are weak π-π stacking inter-actions between symmetry-related pyridine rings with a centroid-centroid distance of 3.807 (1) Å.

Related literature

For background to the insecticidal applications of imidacloprid [systematic name: (E)-1-(6-chloro-3-pyridyl­meth­yl)-N-nitro­imidazolidin-2-yl­idene­amine], see: Deshmukh et al. (2011 ▶, 2012 ▶); Zhao et al. (2010 ▶). For related structures, see: Kapoor et al. (2011 ▶, 2012 ▶); Kant et al. (2012 ▶).

Experimental

Crystal data

C13H16ClN5O4

M = 341.76

Monoclinic,

a = 7.8136 (2) Å

b = 19.3483 (4) Å

c = 10.1926 (2) Å

β = 100.346 (2)°

V = 1515.86 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 293 K

0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2010 ▶) T min = 0.868, T max = 1.000

47458 measured reflections

2983 independent reflections

2387 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.090

S = 1.02

2983 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.29 e Å−3

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681200918X/lh5425sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200918X/lh5425Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681200918X/lh5425Isup3.cml

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

C13H16ClN5O4	F(000) = 712
Mr = 341.76	Dx = 1.498 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 21411 reflections
a = 7.8136 (2) Å	θ = 3.6–29.1°
b = 19.3483 (4) Å	µ = 0.28 mm−1
c = 10.1926 (2) Å	T = 293 K
β = 100.346 (2)°	Plate, white
V = 1515.86 (6) Å3	0.3 × 0.2 × 0.1 mm
Z = 4

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2983 independent reflections
Radiation source: fine-focus sealed tube	2387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.7°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2010)	k = −23→23
Tmin = 0.868, Tmax = 1.000	l = −12→12
47458 measured reflections

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) = 0.090	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0372P)2 + 0.6841P] where P = (Fo2 + 2Fc2)/3
2983 reflections	(Δ/σ)max = 0.001
209 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.IR (cm-1): 3008, 2991, 2908, 1743, 1558, 1548. 1H NMR ?: 1.29(t, J: 7.5 Hz, CH3),3.59(t, J: 7.5 Hz, CH2), 3.84(t, J: 7.5 Hz, CH2), 4.06 (s, CH2), 4.24 (q, J:7.5 Hz, OCH2), 4.50 (s, CH2), 7.37 (d, J: 8.2 Hz, Py1H), 7.74 (dd, J1: 7.5,J2: 2.5 Hz, Py1H), 8.32 (s, Py1H) p.p.m.. LCMS/MS (ESI, m/z): 342.0891 (M+H)+,295.0881, 261.1297, 170.0910.

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.

	x	y	z	Uiso*/Ueq
Cl1	0.49235 (8)	0.34128 (3)	−0.00544 (6)	0.06124 (18)
N1	0.4056 (2)	0.42363 (8)	0.17333 (16)	0.0437 (4)
C2	0.3295 (2)	0.48018 (10)	0.21371 (18)	0.0402 (4)
H2	0.3394	0.4877	0.3049	0.048*
C3	0.2376 (2)	0.52773 (9)	0.12776 (16)	0.0316 (4)
C4	0.2223 (2)	0.51489 (10)	−0.00787 (17)	0.0376 (4)
H4	0.1600	0.5453	−0.0692	0.045*
C5	0.2988 (2)	0.45741 (10)	−0.05220 (18)	0.0406 (4)
H5	0.2903	0.4481	−0.1426	0.049*
C6	0.3884 (2)	0.41447 (10)	0.04397 (19)	0.0387 (4)
C7	0.1554 (2)	0.59159 (10)	0.17545 (16)	0.0362 (4)
H7A	0.1805	0.6309	0.1230	0.043*
H7B	0.0302	0.5855	0.1602	0.043*
N8	0.21587 (18)	0.60656 (8)	0.31527 (14)	0.0337 (3)
C9	0.3777 (2)	0.64367 (10)	0.36251 (18)	0.0377 (4)
H9A	0.3764	0.6890	0.3218	0.045*
H9B	0.4774	0.6180	0.3440	0.045*
C10	0.3805 (2)	0.64912 (11)	0.5113 (2)	0.0459 (5)
H10A	0.4723	0.6208	0.5610	0.055*
H10B	0.3969	0.6966	0.5414	0.055*
N11	0.20831 (18)	0.62338 (7)	0.52662 (14)	0.0314 (3)
C12	0.1228 (2)	0.59805 (8)	0.41189 (16)	0.0278 (3)
N13	−0.02640 (17)	0.56113 (7)	0.38209 (14)	0.0324 (3)
N14	−0.15702 (18)	0.57746 (7)	0.44638 (14)	0.0330 (3)
O15	−0.28030 (16)	0.53623 (7)	0.43068 (15)	0.0490 (4)
O16	−0.15984 (16)	0.63170 (7)	0.51017 (13)	0.0454 (3)
C17	0.1705 (2)	0.61047 (9)	0.65820 (16)	0.0331 (4)
H17A	0.2751	0.5946	0.7165	0.040*
H17B	0.0836	0.5743	0.6531	0.040*
C18	0.1042 (2)	0.67502 (9)	0.71615 (17)	0.0347 (4)
O19	0.13493 (19)	0.73282 (7)	0.68446 (14)	0.0505 (4)
O20	0.01369 (17)	0.65861 (6)	0.81063 (12)	0.0414 (3)
C21	−0.0639 (3)	0.71622 (11)	0.8720 (2)	0.0502 (5)
H21A	0.0215	0.7527	0.8939	0.060*
H21B	−0.0980	0.7007	0.9541	0.060*
C22	−0.2189 (3)	0.74367 (13)	0.7804 (3)	0.0658 (7)
H22A	−0.1828	0.7651	0.7049	0.099*
H22B	−0.2765	0.7772	0.8266	0.099*
H22C	−0.2975	0.7064	0.7505	0.099*

	U11	U22	U33	U12	U13	U23
Cl1	0.0666 (4)	0.0457 (3)	0.0760 (4)	0.0005 (3)	0.0250 (3)	−0.0183 (3)
N1	0.0488 (10)	0.0409 (9)	0.0396 (9)	0.0051 (7)	0.0028 (7)	−0.0019 (7)
C2	0.0482 (11)	0.0440 (11)	0.0273 (9)	0.0050 (9)	0.0036 (8)	−0.0007 (8)
C3	0.0283 (9)	0.0374 (10)	0.0288 (9)	−0.0033 (7)	0.0048 (7)	0.0013 (7)
C4	0.0338 (10)	0.0483 (11)	0.0296 (9)	−0.0034 (8)	0.0025 (7)	0.0026 (8)
C5	0.0402 (10)	0.0523 (12)	0.0296 (9)	−0.0105 (9)	0.0071 (8)	−0.0089 (8)
C6	0.0335 (9)	0.0387 (10)	0.0447 (11)	−0.0064 (8)	0.0089 (8)	−0.0093 (8)
C7	0.0343 (9)	0.0445 (10)	0.0296 (9)	0.0042 (8)	0.0056 (7)	0.0040 (8)
N8	0.0303 (7)	0.0393 (8)	0.0320 (8)	−0.0024 (6)	0.0065 (6)	−0.0023 (6)
C9	0.0274 (9)	0.0414 (10)	0.0443 (10)	−0.0021 (8)	0.0063 (8)	0.0026 (8)
C10	0.0345 (10)	0.0563 (13)	0.0459 (11)	−0.0121 (9)	0.0043 (8)	−0.0037 (9)
N11	0.0316 (7)	0.0311 (8)	0.0309 (7)	−0.0033 (6)	0.0042 (6)	−0.0024 (6)
C12	0.0297 (9)	0.0224 (8)	0.0310 (9)	0.0045 (6)	0.0048 (7)	0.0003 (6)
N13	0.0293 (7)	0.0340 (8)	0.0346 (8)	−0.0030 (6)	0.0074 (6)	−0.0059 (6)
N14	0.0296 (8)	0.0326 (8)	0.0355 (8)	0.0027 (6)	0.0026 (6)	0.0025 (6)
O15	0.0304 (7)	0.0429 (8)	0.0743 (10)	−0.0071 (6)	0.0114 (6)	−0.0031 (7)
O16	0.0414 (7)	0.0428 (8)	0.0529 (8)	0.0053 (6)	0.0104 (6)	−0.0131 (6)
C17	0.0380 (10)	0.0303 (9)	0.0293 (9)	0.0014 (7)	0.0014 (7)	0.0010 (7)
C18	0.0392 (10)	0.0339 (10)	0.0282 (9)	−0.0018 (8)	−0.0013 (7)	−0.0026 (7)
O19	0.0711 (10)	0.0294 (7)	0.0525 (8)	−0.0076 (7)	0.0151 (7)	−0.0041 (6)
O20	0.0550 (8)	0.0366 (7)	0.0345 (7)	0.0050 (6)	0.0127 (6)	−0.0010 (5)
C21	0.0605 (13)	0.0481 (12)	0.0431 (11)	0.0052 (10)	0.0125 (10)	−0.0134 (9)
C22	0.0676 (15)	0.0568 (15)	0.0716 (16)	0.0174 (12)	0.0091 (12)	−0.0097 (12)

Cl1—C6	1.7510 (19)	C10—H10A	0.9700
N1—C6	1.313 (2)	C10—H10B	0.9700
N1—C2	1.345 (2)	N11—C12	1.332 (2)
C2—C3	1.380 (2)	N11—C17	1.446 (2)
C2—H2	0.9300	C12—N13	1.354 (2)
C3—C4	1.388 (2)	N13—N14	1.3458 (19)
C3—C7	1.512 (2)	N14—O16	1.2367 (19)
C4—C5	1.377 (3)	N14—O15	1.2388 (18)
C4—H4	0.9300	C17—C18	1.512 (2)
C5—C6	1.376 (3)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C7—N8	1.448 (2)	C18—O19	1.200 (2)
C7—H7A	0.9700	C18—O20	1.332 (2)
C7—H7B	0.9700	O20—C21	1.462 (2)
N8—C12	1.335 (2)	C21—C22	1.488 (3)
N8—C9	1.459 (2)	C21—H21A	0.9700
C9—C10	1.517 (3)	C21—H21B	0.9700
C9—H9A	0.9700	C22—H22A	0.9600
C9—H9B	0.9700	C22—H22B	0.9600
C10—N11	1.469 (2)	C22—H22C	0.9600
C6—N1—C2	116.47 (16)	C9—C10—H10B	111.1
N1—C2—C3	123.83 (16)	H10A—C10—H10B	109.0
N1—C2—H2	118.1	C12—N11—C17	126.65 (14)
C3—C2—H2	118.1	C12—N11—C10	110.86 (14)
C2—C3—C4	117.05 (16)	C17—N11—C10	120.06 (14)
C2—C3—C7	122.91 (15)	N11—C12—N8	110.38 (14)
C4—C3—C7	120.04 (15)	N11—C12—N13	131.84 (15)
C5—C4—C3	120.43 (17)	N8—C12—N13	117.42 (14)
C5—C4—H4	119.8	N14—N13—C12	117.67 (13)
C3—C4—H4	119.8	O16—N14—O15	121.84 (14)
C6—C5—C4	116.69 (16)	O16—N14—N13	122.81 (14)
C6—C5—H5	121.7	O15—N14—N13	115.21 (14)
C4—C5—H5	121.7	N11—C17—C18	111.17 (14)
N1—C6—C5	125.52 (17)	N11—C17—H17A	109.4
N1—C6—Cl1	115.38 (15)	C18—C17—H17A	109.4
C5—C6—Cl1	119.10 (14)	N11—C17—H17B	109.4
N8—C7—C3	113.43 (14)	C18—C17—H17B	109.4
N8—C7—H7A	108.9	H17A—C17—H17B	108.0
C3—C7—H7A	108.9	O19—C18—O20	125.08 (17)
N8—C7—H7B	108.9	O19—C18—C17	124.43 (17)
C3—C7—H7B	108.9	O20—C18—C17	110.43 (15)
H7A—C7—H7B	107.7	C18—O20—C21	116.27 (15)
C12—N8—C7	125.22 (14)	O20—C21—C22	110.91 (16)
C12—N8—C9	111.84 (14)	O20—C21—H21A	109.5
C7—N8—C9	122.24 (14)	C22—C21—H21A	109.5
N8—C9—C10	102.70 (14)	O20—C21—H21B	109.5
N8—C9—H9A	111.2	C22—C21—H21B	109.5
C10—C9—H9A	111.2	H21A—C21—H21B	108.0
N8—C9—H9B	111.2	C21—C22—H22A	109.5
C10—C9—H9B	111.2	C21—C22—H22B	109.5
H9A—C9—H9B	109.1	H22A—C22—H22B	109.5
N11—C10—C9	103.54 (14)	C21—C22—H22C	109.5
N11—C10—H10A	111.1	H22A—C22—H22C	109.5
C9—C10—H10A	111.1	H22B—C22—H22C	109.5
N11—C10—H10B	111.1
C6—N1—C2—C3	−0.3 (3)	C17—N11—C12—N8	−165.04 (15)
N1—C2—C3—C4	0.9 (3)	C10—N11—C12—N8	−2.9 (2)
N1—C2—C3—C7	−179.01 (17)	C17—N11—C12—N13	7.7 (3)
C2—C3—C4—C5	−0.9 (3)	C10—N11—C12—N13	169.83 (18)
C7—C3—C4—C5	179.07 (16)	C7—N8—C12—N11	−173.32 (15)
C3—C4—C5—C6	0.3 (3)	C9—N8—C12—N11	−2.8 (2)
C2—N1—C6—C5	−0.4 (3)	C7—N8—C12—N13	12.8 (2)
C2—N1—C6—Cl1	178.84 (13)	C9—N8—C12—N13	−176.68 (14)
C4—C5—C6—N1	0.5 (3)	N11—C12—N13—N14	38.2 (3)
C4—C5—C6—Cl1	−178.79 (13)	N8—C12—N13—N14	−149.51 (15)
C2—C3—C7—N8	13.8 (2)	C12—N13—N14—O16	14.3 (2)
C4—C3—C7—N8	−166.19 (15)	C12—N13—N14—O15	−169.90 (15)
C3—C7—N8—C12	−107.54 (18)	C12—N11—C17—C18	−111.85 (18)
C3—C7—N8—C9	82.8 (2)	C10—N11—C17—C18	87.50 (19)
C12—N8—C9—C10	6.9 (2)	N11—C17—C18—O19	−24.7 (2)
C7—N8—C9—C10	177.74 (16)	N11—C17—C18—O20	157.88 (14)
N8—C9—C10—N11	−7.84 (19)	O19—C18—O20—C21	4.8 (3)
C9—C10—N11—C12	7.0 (2)	C17—C18—O20—C21	−177.77 (14)
C9—C10—N11—C17	170.43 (15)	C18—O20—C21—C22	74.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O15i	0.97	2.50	3.358 (2)	147
C17—H17A···N1ii	0.97	2.57	3.509 (2)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O15i	0.97	2.50	3.358 (2)	147
C17—H17A⋯N1ii	0.97	2.57	3.509 (2)	163

Symmetry codes: (i) ; (ii) .