Ethyl 2-{3-[(2-chloro-1,3-thia­zol-5-yl)meth­yl]-4-nitro­imino-1,3,5-triazinan-1-yl}acetate

In the title compound, C₁₁H₁₅ClN₆O₄S, 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 thia­zole ring are oriented at a dihedral angle of 69.62 (8)°. A classical intra­molecular N—H...O hydrogen bond is found in the mol­ecular structure. Moreover, one classical inter­molecular N—H...N and four non-classical C—H...O and C—H...N hydrogen bonds are also present in the crystal structure. Besides inter­molecular hydrogen bonds, the Cl atom forms an inter­molecular short contact [3.020 (2) Å] with one of the nitro O atoms.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.128
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O4      ..       3.02 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         26
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         27

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Neonicotinoid compounds (Tomizawa & Yamamoto, 1993; Kagabu, 1996; Tomizawa et al., 2000) have received much attention on their applications as insecticide (Zhang et al., 2004; Kagabu et al., 2005; Tian et al., 2007). We report here the molecular and crystal structures of the title compound.

The molecular structure of title compound, C₁₁H₁₅ClN₆O₄S, is depicted on Fig.1. The triazine moiety exhibits an opened envolope conformation with N1 out of the envolope plan defined by C5, N3, C7, N2 and C6. The dihedral angle between the thiazole ring and triazine envolope plan is 75.63 (7)°. The planar nitroimine–group and the thiazole ring are oriented the dihedral angle of 69.62 (8)°. The large discrepancy between (O4—N5···N4 115.65 (17)°) and (O3—N5···N4 123.84 (16)°) bond angles attributes to the hydrogen bond effect on O4 and O3 - look the Table 1. Another interesting structure feature that should be mentioned is that the bond lengths (C7—N2 1.340 (2)Å) and (C7—N3 1.329 (2)Å) are between the standard (C—N 1.47Å) single bond and (C═N 1.26Å) double bond, clearly showing the conjugated effect of the nirtoimine. The C7—N4 bond length is as long as to 1.357 (2)Å, due to being linked with a strong electron–attracting nitro–group. Moreover, except intermolecular hydrogen bonding, the crystal structure is further stabilized by the so–called halogen bonding (Riley & Merz, 2007), due to short intermolecular contact of Cl1—O4ⁱ with a distance of 3.020 (2)Å and an angle close to 180° (C11—Cl1···O4ⁱ 178.1 (1)°). Symmetry code: (i) 1-x,1-y,-z).

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).

S2. Experimental

The title compound was prepared by the literature method (Maienfisch et al., (2001). It was purified by silica gel chromatography using ethyl acetate and petroleum ether in the ratio of 1:1, as the flush to afford. This compound was obtained as white crystals, yield 46.7%, ¹H NMR(CDCl₃, 400 Hz): 9.51 (1H, s, NH), 7.44 (1H, s, thiazole—H), 4.61 (2H,s,CH₂—thiazole), 4.48–4.49(4H, d, J = 5.2 Hz, triazine—4H), 4.21–4.15 (2H, m, OCH₂), 3.32 (2H, s, CHC═O) 1.29–1.26 (3H, t, J = 7.2 Hz, CH₃); IR(potassium bromide, cm^-1) 3288(N—H), 3000 (thiazole), 1730 (C═O) 1587 (C═N), 1398 (NO₂), 1224 (C—O—C), 1105 (C—N), Anal. calcd for C₁₁H₁₅ClN₆O₄S: C 36.42, H 4.17, N 23.16; found C 36.40, H 4.23, N 23.19. ESI–MS m/z: 363.8.

S3. Refinement

H atoms bonded to C atoms were positioned geometrically [C—H = 0.93Å (aromatic), 0.97Å (methylene) and 0.96Å (methyl)] and refined in riding modes with U_iso(H) = 1.2U_eq(C) for aromatic and methylene; U_iso(H) = 1.5U~eq~(C) for methyl. H atom bonded to N atom was found from Fourier difference maps and refined with the constraint U_iso(H) = 1.2U_eq(N), but coordinates refined freely.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Spek, 2009).

Figures

Fig. 1. The molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius. The intramolecular H–bond is marked by dashed line.

Ethyl 2-{3-[(2-chloro-1,3-thiazol-5-yl)methyl]- 4-nitroimino-1,3,5-triazinan-1-yl}acetate

Crystal data

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) Å^3	0.40 × 0.23 × 0.20 mm

Data collection

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 monochromator	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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0598P)^2 + 0.0779P] where P = (Fo^2 + 2Fc^2)/3
3259 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.31 e Å^−3
9 restraints	Δρmin = −0.26 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N6^i	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···O3^ii	0.97	2.57	3.191 (3)	122
C5—H5A···N1^iii	0.97	2.61	3.449 (3)	144
C6—H6B···O4^iv	0.97	2.56	3.478 (3)	159
C10—H10···O1^v	0.93	2.45	3.278 (3)	149

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