Ethyl 2-{3-[(2-chloro-1,3-thia-zol-5-yl)meth-yl]-4-nitro-imino-1,3,5-triazinan-1-yl}acetate.

In the title compound, C(11)H(15)ClN(6)O(4)S, which belongs to the neonicotinoid class of insecticidally active heterocyclic compounds, the six-membered triazine ring adopts an opened envolope conformation. The planar nitro imine group [dihedral angle between nitro and imine groups = 1.07 (7)°] and the thia-zole ring are oriented at a dihedral angle of 69.62 (8)°. A classical intra-molecular N-H⋯O hydrogen bond is found in the mol-ecular structure. Moreover, one classical inter-molecular N-H⋯N and four non-classical C-H⋯O and C-H⋯N hydrogen bonds are also present in the crystal structure. Besides inter-molecular hydrogen bonds, the Cl atom forms an inter-molecular short contact [3.020 (2) Å] with one of the nitro O atoms.

Related literature

For general background to neonicotinoid compounds and their application as insecticides, see: Kagabu (1996 ▶); Kagabu et al. (2005 ▶); Tian et al. (2007 ▶); Tomizawa et al. (2000 ▶); Tomizawa & Yamamoto (1993 ▶); Zhang et al. (2004 ▶). For halogen bonding, see: Riley & Merz (2007 ▶). For the synthesis of the title compound, see: Maienfisch et al. (2001 ▶).

Experimental

Crystal data

C11H15ClN6O4S

M = 362.81

Triclinic,

a = 8.5066 (6) Å

b = 9.1114 (7) Å

c = 10.9071 (8) Å

α = 100.488 (2)°

β = 98.416 (3)°

γ = 101.281 (3)°

V = 800.55 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.40 mm−1

T = 298 K

0.40 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.857, T max = 0.925

5350 measured reflections

3259 independent reflections

2670 reflections with I > 2σ(I)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.128

S = 1.05

3259 reflections

212 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810018878/rk2201sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018878/rk2201Isup2.hkl

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

C11H15ClN6O4S	Z = 2
Mr = 362.81	F(000) = 376
Triclinic, P1	Dx = 1.505 Mg m−3
Hall symbol: -P 1	Melting point: 449 K
a = 8.5066 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1114 (7) Å	Cell parameters from 2512 reflections
c = 10.9071 (8) Å	θ = 2.3–28.2°
α = 100.488 (2)°	µ = 0.40 mm−1
β = 98.416 (3)°	T = 298 K
γ = 101.281 (3)°	Block, colourless
V = 800.55 (10) Å3	0.40 × 0.23 × 0.20 mm

Bruker SMART APEX CCD area-detector diffractometer	3259 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2670 reflections with I > 2σ(I)
graphite	Rint = 0.075
Detector resolution: 1.57 × 0.49 mm pixels mm-1	θmax = 26.5°, θmin = 1.9°
0.3° wide ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −10→11
Tmin = 0.857, Tmax = 0.925	l = −13→12
5350 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0598P)2 + 0.0779P] where P = (Fo2 + 2Fc2)/3
3259 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.31 e Å−3
9 restraints	Δρmin = −0.26 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
C1	−0.0095 (3)	0.7149 (2)	0.26414 (19)	0.0444 (5)
H1A	0.0880	0.7030	0.2309	0.053*
H1B	−0.0751	0.7574	0.2054	0.053*
C2	−0.1049 (2)	0.5590 (2)	0.2702 (2)	0.0454 (5)
C3	−0.2096 (4)	0.3054 (3)	0.1509 (3)	0.0701 (7)
H3C	−0.3189	0.3031	0.1674	0.084*
H3B	−0.1526	0.2605	0.2128	0.084*
C4	−0.2173 (5)	0.2185 (3)	0.0216 (3)	0.0943 (11)
H4A	−0.2647	0.2692	−0.0391	0.141*
H4B	−0.2831	0.1169	0.0105	0.141*
H4C	−0.1091	0.2126	0.0092	0.141*
C5	0.1108 (3)	0.9754 (2)	0.3748 (2)	0.0485 (5)
H5A	0.1225	1.0469	0.4549	0.058*
H5B	0.0397	1.0059	0.3108	0.058*
C6	0.1510 (2)	0.7783 (2)	0.47718 (18)	0.0405 (4)
H6A	0.1079	0.6734	0.4825	0.049*
H6B	0.1619	0.8435	0.5603	0.049*
C7	0.3648 (2)	0.88803 (19)	0.36999 (17)	0.0337 (4)
C8	0.4008 (2)	0.6726 (2)	0.46817 (19)	0.0408 (4)
H8A	0.3775	0.6440	0.5462	0.049*
H8B	0.5174	0.7146	0.4805	0.049*
C9	0.3537 (2)	0.5325 (2)	0.36264 (18)	0.0399 (4)
C10	0.2576 (3)	0.3953 (2)	0.3607 (2)	0.0468 (5)
H10	0.2113	0.3768	0.4302	0.056*
C11	0.3072 (3)	0.3403 (2)	0.1709 (2)	0.0527 (6)
Cl1	0.30601 (10)	0.23735 (8)	0.02224 (6)	0.0779 (3)
N1	0.03775 (19)	0.82249 (18)	0.38653 (16)	0.0408 (4)
N2	0.31341 (19)	0.79068 (17)	0.44198 (15)	0.0367 (4)
N3	0.2716 (2)	0.98200 (18)	0.33909 (17)	0.0393 (4)
H3A	0.306 (3)	1.039 (3)	0.297 (2)	0.047*
N4	0.50886 (19)	0.87424 (18)	0.33519 (16)	0.0402 (4)
N5	0.5757 (2)	0.97002 (19)	0.26754 (16)	0.0430 (4)
N6	0.2308 (2)	0.28347 (19)	0.25118 (19)	0.0544 (5)
O1	−0.1559 (2)	0.52487 (19)	0.36034 (15)	0.0659 (5)
O2	−0.1227 (2)	0.46316 (17)	0.16030 (15)	0.0614 (4)
O3	0.5158 (2)	1.0752 (2)	0.23700 (19)	0.0671 (5)
O4	0.70673 (19)	0.95104 (19)	0.23875 (17)	0.0607 (4)
S1	0.41711 (8)	0.52681 (6)	0.21876 (5)	0.0532 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0449 (11)	0.0457 (11)	0.0389 (10)	0.0019 (9)	0.0037 (9)	0.0122 (9)
C2	0.0434 (11)	0.0495 (12)	0.0386 (11)	0.0005 (9)	0.0066 (9)	0.0095 (9)
C3	0.0903 (19)	0.0483 (12)	0.0592 (14)	−0.0107 (12)	0.0183 (13)	0.0055 (11)
C4	0.144 (3)	0.0561 (15)	0.0660 (17)	−0.0045 (17)	0.0236 (19)	−0.0031 (12)
C5	0.0451 (11)	0.0377 (10)	0.0671 (14)	0.0144 (8)	0.0191 (10)	0.0106 (10)
C6	0.0430 (10)	0.0429 (10)	0.0331 (10)	0.0067 (8)	0.0087 (8)	0.0037 (8)
C7	0.0379 (9)	0.0256 (8)	0.0336 (9)	0.0057 (7)	0.0040 (7)	−0.0001 (7)
C8	0.0473 (11)	0.0370 (10)	0.0389 (10)	0.0130 (8)	0.0030 (8)	0.0106 (8)
C9	0.0479 (11)	0.0363 (10)	0.0398 (10)	0.0176 (8)	0.0065 (8)	0.0118 (8)
C10	0.0590 (13)	0.0391 (11)	0.0460 (12)	0.0163 (9)	0.0105 (10)	0.0122 (9)
C11	0.0731 (15)	0.0436 (11)	0.0427 (11)	0.0274 (10)	0.0013 (11)	0.0048 (10)
Cl1	0.1162 (6)	0.0694 (4)	0.0455 (3)	0.0420 (4)	0.0031 (3)	−0.0065 (3)
N1	0.0398 (9)	0.0382 (8)	0.0447 (9)	0.0101 (7)	0.0090 (7)	0.0074 (7)
N2	0.0405 (8)	0.0318 (8)	0.0385 (8)	0.0098 (6)	0.0071 (7)	0.0080 (7)
N3	0.0416 (9)	0.0306 (8)	0.0499 (10)	0.0112 (6)	0.0133 (7)	0.0124 (7)
N4	0.0375 (8)	0.0364 (8)	0.0468 (9)	0.0082 (6)	0.0106 (7)	0.0075 (7)
N5	0.0401 (9)	0.0421 (9)	0.0407 (9)	0.0023 (7)	0.0079 (7)	0.0009 (7)
N6	0.0704 (12)	0.0356 (9)	0.0545 (11)	0.0156 (8)	0.0039 (10)	0.0053 (8)
O1	0.0766 (11)	0.0650 (10)	0.0453 (9)	−0.0146 (8)	0.0207 (8)	0.0100 (8)
O2	0.0806 (11)	0.0484 (9)	0.0455 (9)	−0.0096 (8)	0.0202 (8)	0.0055 (7)
O3	0.0612 (10)	0.0647 (11)	0.0929 (14)	0.0183 (8)	0.0302 (9)	0.0448 (10)
O4	0.0468 (9)	0.0706 (11)	0.0654 (10)	0.0116 (7)	0.0249 (8)	0.0070 (8)
S1	0.0731 (4)	0.0452 (3)	0.0456 (3)	0.0181 (3)	0.0187 (3)	0.0098 (2)

C1—N1	1.455 (3)	C6—H6B	0.9700
C1—C2	1.510 (3)	C7—N3	1.329 (2)
C1—H1A	0.9700	C7—N2	1.340 (2)
C1—H1B	0.9700	C7—N4	1.357 (2)
C2—O1	1.198 (2)	C8—N2	1.468 (2)
C2—O2	1.318 (3)	C8—C9	1.498 (3)
C3—O2	1.460 (3)	C8—H8A	0.9700
C3—C4	1.472 (4)	C8—H8B	0.9700
C3—H3C	0.9700	C9—C10	1.348 (3)
C3—H3B	0.9700	C9—S1	1.728 (2)
C4—H4A	0.9600	C10—N6	1.380 (3)
C4—H4B	0.9600	C10—H10	0.9300
C4—H4C	0.9600	C11—N6	1.287 (3)
C5—N1	1.447 (2)	C11—S1	1.717 (2)
C5—N3	1.469 (3)	C11—Cl1	1.717 (2)
C5—H5A	0.9700	N3—H3A	0.79 (2)
C5—H5B	0.9700	N4—N5	1.339 (2)
C6—N1	1.444 (3)	N5—O4	1.237 (2)
C6—N2	1.476 (2)	N5—O3	1.243 (2)
C6—H6A	0.9700
N1—C1—C2	113.48 (16)	N3—C7—N4	127.89 (17)
N1—C1—H1A	108.9	N2—C7—N4	113.62 (16)
C2—C1—H1A	108.9	N2—C8—C9	112.19 (16)
N1—C1—H1B	108.9	N2—C8—H8A	109.2
C2—C1—H1B	108.9	C9—C8—H8A	109.2
H1A—C1—H1B	107.7	N2—C8—H8B	109.2
O1—C2—O2	124.32 (19)	C9—C8—H8B	109.2
O1—C2—C1	126.2 (2)	H8A—C8—H8B	107.9
O2—C2—C1	109.47 (17)	C10—C9—C8	127.86 (19)
O2—C3—C4	108.0 (2)	C10—C9—S1	109.13 (15)
O2—C3—H3C	110.1	C8—C9—S1	123.00 (14)
C4—C3—H3C	110.1	C9—C10—N6	117.05 (19)
O2—C3—H3B	110.1	C9—C10—H10	121.5
C4—C3—H3B	110.1	N6—C10—H10	121.5
H3C—C3—H3B	108.4	N6—C11—S1	117.24 (17)
C3—C4—H4A	109.5	N6—C11—Cl1	123.01 (18)
C3—C4—H4B	109.5	S1—C11—Cl1	119.74 (15)
H4A—C4—H4B	109.5	C6—N1—C5	107.68 (16)
C3—C4—H4C	109.5	C6—N1—C1	113.41 (16)
H4A—C4—H4C	109.5	C5—N1—C1	111.93 (16)
H4B—C4—H4C	109.5	C7—N2—C8	121.33 (16)
N1—C5—N3	111.07 (15)	C7—N2—C6	120.93 (15)
N1—C5—H5A	109.4	C8—N2—C6	116.72 (15)
N3—C5—H5A	109.4	C7—N3—C5	122.00 (17)
N1—C5—H5B	109.4	C7—N3—H3A	115.8 (16)
N3—C5—H5B	109.4	C5—N3—H3A	122.2 (16)
H5A—C5—H5B	108.0	N5—N4—C7	118.95 (16)
N1—C6—N2	112.02 (15)	O4—N5—O3	120.48 (17)
N1—C6—H6A	109.2	O4—N5—N4	115.65 (17)
N2—C6—H6A	109.2	O3—N5—N4	123.84 (16)
N1—C6—H6B	109.2	C11—N6—C10	108.32 (18)
N2—C6—H6B	109.2	C2—O2—C3	116.56 (17)
H6A—C6—H6B	107.9	C11—S1—C9	88.24 (10)
N3—C7—N2	118.48 (17)
N1—C1—C2—O1	7.9 (3)	N1—C6—N2—C8	−143.03 (17)
N1—C1—C2—O2	−171.21 (18)	N2—C7—N3—C5	−3.8 (3)
N2—C8—C9—C10	−105.2 (2)	N4—C7—N3—C5	174.62 (18)
N2—C8—C9—S1	73.8 (2)	N1—C5—N3—C7	−28.0 (3)
C8—C9—C10—N6	179.47 (18)	N3—C7—N4—N5	4.3 (3)
S1—C9—C10—N6	0.3 (2)	N2—C7—N4—N5	−177.22 (16)
N2—C6—N1—C5	−55.1 (2)	C7—N4—N5—O4	−179.85 (17)
N2—C6—N1—C1	69.28 (19)	C7—N4—N5—O3	2.1 (3)
N3—C5—N1—C6	56.0 (2)	S1—C11—N6—C10	0.8 (2)
N3—C5—N1—C1	−69.3 (2)	Cl1—C11—N6—C10	179.62 (16)
C2—C1—N1—C6	65.1 (2)	C9—C10—N6—C11	−0.7 (3)
C2—C1—N1—C5	−172.82 (16)	O1—C2—O2—C3	−0.5 (4)
N3—C7—N2—C8	173.29 (16)	C1—C2—O2—C3	178.7 (2)
N4—C7—N2—C8	−5.4 (2)	C4—C3—O2—C2	179.5 (2)
N3—C7—N2—C6	5.2 (3)	N6—C11—S1—C9	−0.57 (19)
N4—C7—N2—C6	−173.49 (16)	Cl1—C11—S1—C9	−179.41 (14)
C9—C8—N2—C7	−82.8 (2)	C10—C9—S1—C11	0.11 (16)
C9—C8—N2—C6	85.8 (2)	C8—C9—S1—C11	−179.09 (17)
N1—C6—N2—C7	25.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N6i	0.79 (2)	2.55 (2)	3.133 (2)	132 (2)
N3—H3A···O3	0.79 (2)	1.98 (2)	2.570 (2)	131 (2)
C3—H3C···O3ii	0.97	2.57	3.191 (3)	122
C5—H5A···N1iii	0.97	2.61	3.449 (3)	144
C6—H6B···O4iv	0.97	2.56	3.478 (3)	159
C10—H10···O1v	0.93	2.45	3.278 (3)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N6i	0.79 (2)	2.55 (2)	3.133 (2)	132 (2)
N3—H3A⋯O3	0.79 (2)	1.98 (2)	2.570 (2)	131 (2)
C3—H3C⋯O3ii	0.97	2.57	3.191 (3)	122
C5—H5A⋯N1iii	0.97	2.61	3.449 (3)	144
C6—H6B⋯O4iv	0.97	2.56	3.478 (3)	159
C10—H10⋯O1v	0.93	2.45	3.278 (3)	149

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .