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organic compounds
1-(2-Chloro-1,3-thiazol-5-ylmethyl)-3,5-dimethyl-2-nitrimino-1,2,3,4,5,6-hexahydro-1,3,5-triazine
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
In the title compound, C9H13ClN6O2S, all bond lengths and angles are normal. The 1,3,5-triazine ring exhibits a half-chair conformation. In the weak intermolecular C—H⋯N and C—H⋯O hydrogen bonds link the molecules into layers parallel to the bc plane.
Related literature
For synthesis of the title compound, see: Frank et al. (1990). For related crystal structures, see: Zurn et al. (1982
). For useful applications of related compounds, see: Motohiro (2000
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: RAPID-AUTO (Rigaku 2004); cell RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2001
); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536807062071/cv2360sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062071/cv2360Isup2.hkl
1,5-Dimethyl-2-nitroiminohexahydro-1,3,5-triazine1.72 g (0.01 mol) was dissolved in 20 ml of dried DMF. To the solution, 60% sodium hydride 0.28 g(0.012 mol) was added portionwise with cooling. The mixture was stirred for 1 h at room temperature until evolution of hydrogen was ceased and then the mixture was heated with strring further for 1 h at 50° C. To the mixture, a solution of 2-chloro-5-thiazolymethylchloride1.72 g (0.01 mol) in 8 ml of dried DMF was added dropwise at 40–50° C. After this additon,the reaction mixture was heated with strring for two hours at 70–80° C. The mixture was poured into ice-water and extracted with dichloromethane. The extract was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off. The residue was purified by a
to obtain the title compound(0.82 g, yield 27%).(Frank et al., 1990). Single crystals suitable for X-ray measurement were obtained by recrystallization from dichloromethane at room temperature.All H atoms were placed in idealized positions and constrained to ride on their parent atoms (C—H 0.93–0.97 Å), with Uiso(H) values set at 1.5 Ueq(C)(for CH3) or 1.2 Ueq(C)(for CH2, thiazole CH).
Crop protection and veterinary pest control have changed greatly with the recent introduction of neonicotinoid insecticides represented by imidacloprid, the only major new class of chemical insecticides of the last three decades. They are increasingly utilized throughout the world (billion-dollar-a-year market), and seven neonicotinoid insecticide are commercialized or nearly on the market at present and expected to become fourth major insecticide group following the organophosphates, methylcarbamates and pyrethroids (Motohiro, 2000). Clothianidin is a neonicotinoid insecticide that was synthesized in Japan by Takeda Chemical. The title compound (I) was synthesized as an intermediate for the synthesis of clothianidin. We report here the
of (I).In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Zurn et al., 1982). The title compound contains three planar fragments, which includes thiazole ring C1—C3/N1/S1 and a triazine ring C5—C7/N2/N3. The triazine ring forms two planes - C5/C6/C7/N2 and N3/C5/C7, respectively, with a dihedral angle of 50.8 (2)° between them. The
is stabilized by intermolecular C—H···O and N—H···O hydrogen bonds (Table 1, Fig. 2).For synthesis of the title compound, see: Frank et al. (1990). For related crystal structures, see: Zurn et al. (1982). For useful applications of related compounds, see: Motohiro (2000).
Data collection: RAPID-AUTO (Rigaku 2004); cell
RAPID-AUTO (Rigaku 2004); data reduction: RAPID-AUTO (Rigaku 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001). ![]() | Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 30% probability level. |
![]() | Fig. 2. A packing diagram viewed down the b axis. Hydrogen bonds are shown as dashed lines. |
C9H13ClN6O2S | F(000) = 1264 |
Mr = 304.76 | Dx = 1.513 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2652 reflections |
a = 32.864 (7) Å | θ = 2.6–25.6° |
b = 6.4063 (13) Å | µ = 0.45 mm−1 |
c = 13.569 (3) Å | T = 293 K |
β = 110.53 (3)° | Block, colourless |
V = 2675.3 (11) Å3 | 0.32 × 0.22 × 0.10 mm |
Z = 8 |
Rigaku R-AXIS RAPID IP area-detector diffractometer | 2363 independent reflections |
Radiation source: Rotating Anode | 1985 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω Oscillation scans | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (ABSCOR; Higashi 1995) | h = −38→38 |
Tmin = 0.869, Tmax = 0.956 | k = −7→7 |
9419 measured reflections | l = −16→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0788P)2 + 1.7911P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max < 0.001 |
2363 reflections | Δρmax = 0.38 e Å−3 |
173 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0107 (11) |
C9H13ClN6O2S | V = 2675.3 (11) Å3 |
Mr = 304.76 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 32.864 (7) Å | µ = 0.45 mm−1 |
b = 6.4063 (13) Å | T = 293 K |
c = 13.569 (3) Å | 0.32 × 0.22 × 0.10 mm |
β = 110.53 (3)° |
Rigaku R-AXIS RAPID IP area-detector diffractometer | 2363 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi 1995) | 1985 reflections with I > 2σ(I) |
Tmin = 0.869, Tmax = 0.956 | Rint = 0.033 |
9419 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.17 | Δρmax = 0.38 e Å−3 |
2363 reflections | Δρmin = −0.33 e Å−3 |
173 parameters |
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 | ||
S1 | 0.06171 (2) | 0.27878 (12) | 0.16669 (7) | 0.0561 (3) | |
Cl1 | −0.03042 (2) | 0.41507 (14) | 0.09448 (8) | 0.0715 (3) | |
C1 | 0.00747 (8) | 0.2188 (4) | 0.1269 (2) | 0.0456 (6) | |
N1 | −0.00266 (8) | 0.0260 (4) | 0.1214 (2) | 0.0551 (6) | |
O1 | 0.15917 (9) | 0.4743 (4) | 0.2334 (2) | 0.0874 (9) | |
N2 | 0.14362 (6) | −0.0081 (3) | 0.15051 (14) | 0.0355 (5) | |
C2 | 0.03521 (9) | −0.0889 (5) | 0.1509 (2) | 0.0541 (7) | |
H2A | 0.0346 | −0.2340 | 0.1520 | 0.065* | |
O2 | 0.19505 (9) | 0.4278 (4) | 0.40121 (19) | 0.0825 (8) | |
N3 | 0.14082 (7) | 0.0518 (3) | −0.02674 (15) | 0.0415 (5) | |
C3 | 0.07300 (8) | 0.0158 (4) | 0.17781 (18) | 0.0378 (6) | |
N4 | 0.20026 (6) | 0.1676 (3) | 0.12543 (16) | 0.0403 (5) | |
C4 | 0.11820 (8) | −0.0718 (4) | 0.21546 (19) | 0.0408 (6) | |
H4A | 0.1332 | −0.0265 | 0.2873 | 0.049* | |
H4B | 0.1165 | −0.2230 | 0.2157 | 0.049* | |
N5 | 0.19224 (7) | 0.1754 (3) | 0.29169 (16) | 0.0456 (6) | |
C5 | 0.13045 (9) | −0.0922 (4) | 0.04226 (19) | 0.0470 (7) | |
H5B | 0.1452 | −0.2236 | 0.0432 | 0.056* | |
H5C | 0.0994 | −0.1189 | 0.0160 | 0.056* | |
C6 | 0.17769 (7) | 0.1185 (4) | 0.18622 (17) | 0.0333 (5) | |
N6 | 0.18187 (8) | 0.3633 (4) | 0.30871 (19) | 0.0527 (6) | |
C7 | 0.18655 (8) | 0.0946 (4) | 0.01513 (19) | 0.0454 (6) | |
H7A | 0.1935 | 0.2005 | −0.0275 | 0.054* | |
H7B | 0.2025 | −0.0311 | 0.0118 | 0.054* | |
C8 | 0.11418 (10) | 0.2411 (5) | −0.0471 (2) | 0.0559 (8) | |
H8A | 0.1225 | 0.3313 | −0.0932 | 0.084* | |
H8B | 0.1184 | 0.3120 | 0.0181 | 0.084* | |
H8C | 0.0841 | 0.2041 | −0.0795 | 0.084* | |
C9 | 0.23765 (9) | 0.3080 (5) | 0.1597 (3) | 0.0594 (8) | |
H9A | 0.2435 | 0.3482 | 0.2315 | 0.089* | |
H9B | 0.2315 | 0.4301 | 0.1159 | 0.089* | |
H9C | 0.2626 | 0.2380 | 0.1541 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0366 (4) | 0.0366 (4) | 0.0967 (6) | −0.0027 (3) | 0.0252 (4) | −0.0049 (3) |
Cl1 | 0.0430 (4) | 0.0628 (6) | 0.1085 (7) | 0.0110 (3) | 0.0262 (4) | 0.0014 (4) |
C1 | 0.0374 (13) | 0.0489 (16) | 0.0538 (15) | −0.0002 (12) | 0.0200 (12) | −0.0001 (12) |
N1 | 0.0405 (12) | 0.0520 (15) | 0.0704 (15) | −0.0082 (11) | 0.0165 (11) | 0.0040 (12) |
O1 | 0.105 (2) | 0.0537 (14) | 0.0933 (18) | 0.0394 (15) | 0.0215 (16) | −0.0055 (13) |
N2 | 0.0382 (11) | 0.0361 (11) | 0.0352 (10) | −0.0033 (9) | 0.0167 (8) | −0.0010 (8) |
C2 | 0.0520 (17) | 0.0361 (15) | 0.0735 (18) | −0.0093 (12) | 0.0211 (14) | 0.0036 (13) |
O2 | 0.1016 (19) | 0.0792 (18) | 0.0685 (14) | −0.0091 (14) | 0.0320 (13) | −0.0434 (13) |
N3 | 0.0451 (12) | 0.0470 (13) | 0.0362 (10) | −0.0016 (10) | 0.0188 (9) | −0.0025 (9) |
C3 | 0.0409 (13) | 0.0387 (14) | 0.0375 (12) | −0.0007 (11) | 0.0183 (10) | 0.0041 (10) |
N4 | 0.0339 (10) | 0.0429 (12) | 0.0461 (11) | −0.0048 (9) | 0.0165 (9) | −0.0043 (9) |
C4 | 0.0444 (14) | 0.0400 (14) | 0.0426 (13) | 0.0043 (11) | 0.0209 (11) | 0.0103 (11) |
N5 | 0.0539 (14) | 0.0410 (12) | 0.0371 (11) | 0.0073 (10) | 0.0098 (10) | −0.0071 (9) |
C5 | 0.0559 (16) | 0.0464 (16) | 0.0426 (13) | −0.0155 (13) | 0.0223 (12) | −0.0121 (11) |
C6 | 0.0331 (12) | 0.0303 (12) | 0.0352 (11) | 0.0089 (10) | 0.0104 (9) | 0.0018 (9) |
N6 | 0.0506 (13) | 0.0488 (14) | 0.0603 (14) | 0.0043 (12) | 0.0213 (11) | −0.0158 (12) |
C7 | 0.0460 (14) | 0.0533 (16) | 0.0440 (13) | −0.0004 (12) | 0.0247 (11) | −0.0040 (11) |
C8 | 0.0573 (18) | 0.067 (2) | 0.0438 (14) | 0.0142 (15) | 0.0177 (13) | 0.0042 (13) |
C9 | 0.0440 (15) | 0.064 (2) | 0.0733 (19) | −0.0178 (14) | 0.0239 (14) | −0.0106 (15) |
S1—C1 | 1.715 (3) | N4—C9 | 1.461 (3) |
S1—C3 | 1.720 (3) | N4—C7 | 1.479 (3) |
Cl1—C1 | 1.715 (3) | C4—H4A | 0.9700 |
C1—N1 | 1.275 (4) | C4—H4B | 0.9700 |
N1—C2 | 1.379 (4) | N5—N6 | 1.294 (3) |
O1—N6 | 1.254 (3) | N5—C6 | 1.389 (3) |
N2—C6 | 1.329 (3) | C5—H5B | 0.9700 |
N2—C4 | 1.469 (3) | C5—H5C | 0.9700 |
N2—C5 | 1.480 (3) | C7—H7A | 0.9700 |
C2—C3 | 1.344 (4) | C7—H7B | 0.9700 |
C2—H2A | 0.9300 | C8—H8A | 0.9600 |
O2—N6 | 1.246 (3) | C8—H8B | 0.9600 |
N3—C7 | 1.434 (3) | C8—H8C | 0.9600 |
N3—C5 | 1.438 (3) | C9—H9A | 0.9600 |
N3—C8 | 1.464 (3) | C9—H9B | 0.9600 |
C3—C4 | 1.500 (3) | C9—H9C | 0.9600 |
N4—C6 | 1.326 (3) | ||
C1—S1—C3 | 88.66 (13) | N2—C5—H5B | 109.4 |
N1—C1—Cl1 | 123.0 (2) | N3—C5—H5C | 109.4 |
N1—C1—S1 | 117.2 (2) | N2—C5—H5C | 109.4 |
Cl1—C1—S1 | 119.85 (17) | H5B—C5—H5C | 108.0 |
C1—N1—C2 | 108.0 (2) | N4—C6—N2 | 120.1 (2) |
C6—N2—C4 | 122.32 (19) | N4—C6—N5 | 120.9 (2) |
C6—N2—C5 | 120.00 (19) | N2—C6—N5 | 118.5 (2) |
C4—N2—C5 | 117.67 (19) | O2—N6—O1 | 122.0 (3) |
C3—C2—N1 | 117.8 (3) | O2—N6—N5 | 117.9 (3) |
C3—C2—H2A | 121.1 | O1—N6—N5 | 120.1 (2) |
N1—C2—H2A | 121.1 | N3—C7—N4 | 111.47 (19) |
C7—N3—C5 | 108.6 (2) | N3—C7—H7A | 109.3 |
C7—N3—C8 | 113.0 (2) | N4—C7—H7A | 109.3 |
C5—N3—C8 | 113.1 (2) | N3—C7—H7B | 109.3 |
C2—C3—C4 | 128.0 (3) | N4—C7—H7B | 109.3 |
C2—C3—S1 | 108.3 (2) | H7A—C7—H7B | 108.0 |
C4—C3—S1 | 123.62 (19) | N3—C8—H8A | 109.5 |
C6—N4—C9 | 122.7 (2) | N3—C8—H8B | 109.5 |
C6—N4—C7 | 121.1 (2) | H8A—C8—H8B | 109.5 |
C9—N4—C7 | 116.1 (2) | N3—C8—H8C | 109.5 |
N2—C4—C3 | 113.29 (19) | H8A—C8—H8C | 109.5 |
N2—C4—H4A | 108.9 | H8B—C8—H8C | 109.5 |
C3—C4—H4A | 108.9 | N4—C9—H9A | 109.5 |
N2—C4—H4B | 108.9 | N4—C9—H9B | 109.5 |
C3—C4—H4B | 108.9 | H9A—C9—H9B | 109.5 |
H4A—C4—H4B | 107.7 | N4—C9—H9C | 109.5 |
N6—N5—C6 | 114.3 (2) | H9A—C9—H9C | 109.5 |
N3—C5—N2 | 111.0 (2) | H9B—C9—H9C | 109.5 |
N3—C5—H5B | 109.4 | ||
C3—S1—C1—N1 | 0.1 (2) | C9—N4—C6—N2 | 179.1 (2) |
C3—S1—C1—Cl1 | −178.89 (18) | C7—N4—C6—N2 | 4.0 (3) |
Cl1—C1—N1—C2 | 178.9 (2) | C9—N4—C6—N5 | −9.2 (4) |
S1—C1—N1—C2 | −0.1 (3) | C7—N4—C6—N5 | 175.6 (2) |
C1—N1—C2—C3 | 0.0 (4) | C4—N2—C6—N4 | 178.4 (2) |
N1—C2—C3—C4 | 178.0 (2) | C5—N2—C6—N4 | −0.8 (3) |
N1—C2—C3—S1 | 0.1 (3) | C4—N2—C6—N5 | 6.5 (3) |
C1—S1—C3—C2 | −0.1 (2) | C5—N2—C6—N5 | −172.7 (2) |
C1—S1—C3—C4 | −178.1 (2) | N6—N5—C6—N4 | 84.1 (3) |
C6—N2—C4—C3 | 112.1 (3) | N6—N5—C6—N2 | −104.1 (3) |
C5—N2—C4—C3 | −68.7 (3) | C6—N5—N6—O2 | −177.7 (2) |
C2—C3—C4—N2 | 123.3 (3) | C6—N5—N6—O1 | 2.4 (4) |
S1—C3—C4—N2 | −59.1 (3) | C5—N3—C7—N4 | −54.3 (3) |
C7—N3—C5—N2 | 57.2 (3) | C8—N3—C7—N4 | 72.1 (3) |
C8—N3—C5—N2 | −69.0 (3) | C6—N4—C7—N3 | 24.6 (3) |
C6—N2—C5—N3 | −30.6 (3) | C9—N4—C7—N3 | −150.9 (2) |
C4—N2—C5—N3 | 150.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···N3i | 0.97 | 2.45 | 3.314 (3) | 148 |
C4—H4B···O1ii | 0.97 | 2.36 | 3.178 (3) | 142 |
C7—H7A···O2iii | 0.97 | 2.58 | 3.483 (4) | 156 |
Symmetry codes: (i) x, −y, z+1/2; (ii) x, y−1, z; (iii) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H13ClN6O2S |
Mr | 304.76 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 32.864 (7), 6.4063 (13), 13.569 (3) |
β (°) | 110.53 (3) |
V (Å3) | 2675.3 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.32 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID IP area-detector |
Absorption correction | Multi-scan (ABSCOR; Higashi 1995) |
Tmin, Tmax | 0.869, 0.956 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9419, 2363, 1985 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.145, 1.17 |
No. of reflections | 2363 |
No. of parameters | 173 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.33 |
Computer programs: RAPID-AUTO (Rigaku 2004), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···N3i | 0.97 | 2.45 | 3.314 (3) | 147.9 |
C4—H4B···O1ii | 0.97 | 2.36 | 3.178 (3) | 142.2 |
C7—H7A···O2iii | 0.97 | 2.58 | 3.483 (4) | 155.5 |
Symmetry codes: (i) x, −y, z+1/2; (ii) x, y−1, z; (iii) x, −y+1, z−1/2. |
References
Frank, W., Noriyoshi, K., Kiyoshi, T., Shigenori, S. & Junko, S. (1990). EP Patent 0 428 941. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Motohiro, T. (2000). Pestic. Outlook, 6, 238–240. Google Scholar
Rigaku (2004). RAPID-AUTO. Version 3.0. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Zurn, V., Schwarz, W., Rozdzinski, W. & Schmidt, A. (1982). Z. Naturforsch. Teil B, 37, 81–85. Google Scholar
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Crop protection and veterinary pest control have changed greatly with the recent introduction of neonicotinoid insecticides represented by imidacloprid, the only major new class of chemical insecticides of the last three decades. They are increasingly utilized throughout the world (billion-dollar-a-year market), and seven neonicotinoid insecticide are commercialized or nearly on the market at present and expected to become fourth major insecticide group following the organophosphates, methylcarbamates and pyrethroids (Motohiro, 2000). Clothianidin is a neonicotinoid insecticide that was synthesized in Japan by Takeda Chemical. The title compound (I) was synthesized as an intermediate for the synthesis of clothianidin. We report here the crystal structure of (I).
In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Zurn et al., 1982). The title compound contains three planar fragments, which includes thiazole ring C1—C3/N1/S1 and a triazine ring C5—C7/N2/N3. The triazine ring forms two planes - C5/C6/C7/N2 and N3/C5/C7, respectively, with a dihedral angle of 50.8 (2)° between them. The crystal structure is stabilized by intermolecular C—H···O and N—H···O hydrogen bonds (Table 1, Fig. 2).