3-[(2-Chloro-1,3-thia­zol-5-yl)meth­yl]-5-methyl-1,3,5-oxadiazinan-4-one

Kant, R.; Gupta, V.K.; Kapoor, K.; Shripanavar, C.S.; Banerjee, K.

doi:10.1107/S1600536812042031

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3109

doi:10.1107/S1600536812042031

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3-[(2-Chloro-1,3-thiazol-5-yl)methyl]-5-methyl-1,3,5-oxadiazinan-4-one

Rajni Kant,^a ^* Vivek K. Gupta,^a Kamini Kapoor,^a Chetan S. Shripanavar ^b and Kaushik Banerjee ^b

^aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and ^bNational Research Centre for Grapes, Pune 412 307, India
^*Correspondence e-mail: rkvk.paper11@gmail.com

(Received 12 September 2012; accepted 8 October 2012; online 13 October 2012)

In the title compound, C₈H₁₀ClN₃O₂S, the oxadiazinane ring is in a sofa conformation with the ring O atom deviating from the best plane of the remaining five atoms by 0.636 (2) Å. A short intramolecular C-S⋯O=C contact [S⋯O 3.122 (2) Å, C—S⋯O 80.0 (2)°] is observed between the two molecular fragments bridged by the methylene group. In the crystal, C—H⋯O hydrogen bonds link molecules, forming chains along the b axis.

Related literature

For the biological activity of thiamethoxam, see: Maienfisch et al. (2001 , 2006 ); Suchail et al. (2001 ); Ford & Casida (2006 ). For the structure of thiamethoxam, see: Chopra et al. (2004 ). For ring conformations, see: Duax & Norton (1975 ).

Experimental

Crystal data

C₈H₁₀ClN₃O₂S
M_r = 247.70
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.6141 (2) Å
b = 11.7335 (4) Å
c = 20.1460 (8) Å
V = 1090.70 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.925, T_max = 1.000
22323 measured reflections
2147 independent reflections
1974 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.081
S = 1.07
2147 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 856 Friedel pairs
Flack parameter: 0.04 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O7ⁱ	0.93	2.60	3.443 (3)	151
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536812042031/gk2519sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042031/gk2519Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812042031/gk2519Isup3.cml

checkCIF report

Comment top

An important milestone in the history of modern insect control is marked by the discovery of neonicotinoid insecticides (Maienfisch, 2006). In 1998 Novartis launched thiamethoxam as a novel second generation neonicotinoid with a unique structure and outstanding insecticidal activity (Maienfisch et al., 2001). The major natural metabolite of thiamethoxam is the title compound, which is thiamethoxam urea derivative (Suchail et al., 2001, Ford & Casida, 2006)

In the title compound (Fig.1) all bond lengths and angles are normal and correspond to those observed in the related structure (Chopra et al., 2004). The oxadiazinane ring is in a sofa conformation [asymmetry parameter: ΔCs(O1—C4) = 7.47 (Duax & Norton, 1975)]. In the crystal, the displacement of the atom O1 from the plane defined by atoms C2/N3/C4/N5/C6 is -0.636 (2) Å. In thiametoxam and the title compound the two molecular fragments bridged by the methylene group are similarly oriented. C—H···O hydrogen bonds link molecules to form chains along b axis(Fig.2).

Related literature top

For the biological activity of thiamethoxam, see: Maienfisch et al. (2001, 2006); Suchail et al. (2001); Ford & Casida (2006). For the structure of thiamethoxam, see: Chopra et al. (2004). For ring conformations, see: Duax & Norton (1975).

Experimental top

Thiamethoxam (0.291 g, 0.001 mol) was dissolved in 5 ml methanol and to it 5 ml of 1 N K₂CO₃ solution was added. The reaction mixture was refluxed for about 10 h on a water bath at 343 K and then cooled. The reaction mixture was neutralized with 1 N HCl solution, until the solid compound was separated out. The synthesized compound was dissolved in minimum amount of methanol and was kept standing for slow evaporation until colourless transparent crystals were formed (m.p. = 372 K).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (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); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The thermal ellipsoids are drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing arrangement of molecules viewed down the a axis. The dotted lines show intermolecular C—H···O hydrogen bonds.

3-[(2-Chloro-1,3-thiazol-5-yl)methyl]-5-methyl-1,3,5-oxadiazinan-4-one top

Crystal data top

C₈H₁₀ClN₃O₂S	F(000) = 512
M_r = 247.70	D_x = 1.508 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11280 reflections
a = 4.6141 (2) Å	θ = 3.5–29.0°
b = 11.7335 (4) Å	µ = 0.53 mm⁻¹
c = 20.1460 (8) Å	T = 293 K
V = 1090.70 (7) Å³	Needle, white
Z = 4	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2147 independent reflections
Radiation source: fine-focus sealed tube	1974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.1049 pixels mm^-1	θ_max = 26.0°, θ_min = 3.5°
ω scan	h = −5→5
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −14→14
T_min = 0.925, T_max = 1.000	l = −24→24
22323 measured reflections

Refinement top

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0399P)² + 0.2799P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2147 reflections	Δρ_max = 0.22 e Å⁻³
137 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 856 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (9)

Crystal data top

C₈H₁₀ClN₃O₂S	V = 1090.70 (7) Å³
M_r = 247.70	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.6141 (2) Å	µ = 0.53 mm⁻¹
b = 11.7335 (4) Å	T = 293 K
c = 20.1460 (8) Å	0.3 × 0.2 × 0.2 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2147 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1974 reflections with I > 2σ(I)
T_min = 0.925, T_max = 1.000	R_int = 0.034
22323 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.081	Δρ_max = 0.22 e Å⁻³
S = 1.07	Δρ_min = −0.16 e Å⁻³
2147 reflections	Absolute structure: Flack (1983), 856 Friedel pairs
137 parameters	Absolute structure parameter: 0.04 (9)
0 restraints

Special details top

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.

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
S1	0.29172 (13)	0.85031 (5)	0.83926 (3)	0.04611 (15)
Cl1	0.64157 (15)	0.83860 (6)	0.96232 (3)	0.0642 (2)
O1	0.4809 (4)	1.08899 (16)	0.64448 (10)	0.0653 (5)
C2	0.2262 (7)	1.1021 (2)	0.68003 (16)	0.0668 (8)
H2A	0.0844	1.1412	0.6527	0.080*
H2B	0.2630	1.1487	0.7189	0.080*
N3	0.1108 (5)	0.99332 (17)	0.70052 (10)	0.0512 (5)
C4	0.1836 (6)	0.8940 (2)	0.67011 (12)	0.0516 (6)
N5	0.3433 (6)	0.90503 (19)	0.61443 (11)	0.0640 (6)
C6	0.4364 (9)	1.0158 (3)	0.59173 (14)	0.0778 (9)
H6A	0.6149	1.0079	0.5667	0.093*
H6B	0.2905	1.0475	0.5624	0.093*
C7	−0.0657 (6)	0.9905 (3)	0.76014 (14)	0.0613 (7)
H7A	−0.2048	0.9289	0.7564	0.074*
H7B	−0.1734	1.0613	0.7634	0.074*
O7	0.1066 (5)	0.80128 (15)	0.69297 (10)	0.0744 (6)
C8	0.4470 (9)	0.8075 (3)	0.57872 (19)	0.0975 (12)
H8A	0.3872	0.7392	0.6012	0.146*
H8B	0.6547	0.8098	0.5765	0.146*
H8C	0.3684	0.8080	0.5346	0.146*
C9	0.1052 (5)	0.9747 (2)	0.82176 (12)	0.0494 (6)
C10	0.4123 (5)	0.9127 (2)	0.91085 (12)	0.0484 (6)
N11	0.3276 (6)	1.01443 (19)	0.92255 (12)	0.0692 (7)
C12	0.1516 (7)	1.0488 (2)	0.87096 (15)	0.0680 (8)
H12	0.0683	1.1210	0.8704	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0529 (3)	0.0353 (2)	0.0501 (3)	0.0000 (2)	0.0022 (2)	0.0000 (2)
Cl1	0.0651 (4)	0.0728 (4)	0.0546 (4)	−0.0027 (4)	−0.0063 (3)	0.0091 (3)
O1	0.0633 (11)	0.0579 (11)	0.0748 (12)	−0.0128 (9)	−0.0003 (10)	0.0120 (10)
C2	0.0732 (18)	0.0395 (12)	0.088 (2)	0.0011 (13)	0.0047 (16)	0.0129 (13)
N3	0.0552 (12)	0.0421 (10)	0.0563 (12)	−0.0002 (9)	0.0042 (10)	0.0105 (9)
C4	0.0570 (13)	0.0446 (11)	0.0533 (14)	−0.0083 (11)	−0.0123 (13)	0.0084 (11)
N5	0.0871 (17)	0.0551 (13)	0.0499 (12)	−0.0056 (13)	0.0064 (12)	−0.0020 (10)
C6	0.102 (3)	0.079 (2)	0.0529 (17)	−0.0165 (19)	0.0084 (16)	0.0135 (15)
C7	0.0480 (14)	0.0691 (16)	0.0669 (17)	0.0082 (13)	0.0019 (12)	0.0110 (14)
O7	0.1021 (17)	0.0435 (9)	0.0775 (13)	−0.0221 (11)	−0.0017 (13)	0.0082 (9)
C8	0.121 (3)	0.089 (2)	0.083 (2)	0.003 (2)	0.011 (2)	−0.025 (2)
C9	0.0472 (13)	0.0450 (12)	0.0561 (14)	0.0058 (10)	0.0112 (11)	0.0061 (11)
C10	0.0505 (13)	0.0459 (13)	0.0487 (13)	−0.0061 (11)	0.0058 (11)	0.0009 (10)
N11	0.0892 (19)	0.0501 (12)	0.0683 (15)	0.0053 (13)	0.0002 (14)	−0.0144 (11)
C12	0.087 (2)	0.0429 (14)	0.0741 (19)	0.0176 (14)	0.0026 (17)	−0.0061 (12)

Geometric parameters (Å, º) top

S1—C10	1.710 (2)	N5—C6	1.443 (4)
S1—C9	1.731 (2)	C6—H6A	0.9700
Cl1—C10	1.718 (3)	C6—H6B	0.9700
O1—C6	1.382 (4)	C7—C9	1.482 (4)
O1—C2	1.385 (4)	C7—H7A	0.9700
C2—N3	1.443 (3)	C7—H7B	0.9700
C2—H2A	0.9700	C8—H8A	0.9600
C2—H2B	0.9700	C8—H8B	0.9600
N3—C4	1.359 (3)	C8—H8C	0.9600
N3—C7	1.452 (3)	C9—C12	1.336 (4)
C4—O7	1.233 (3)	C10—N11	1.278 (3)
C4—N5	1.348 (3)	N11—C12	1.379 (4)
N5—C8	1.434 (4)	C12—H12	0.9300

C10—S1—C9	88.42 (12)	N3—C7—C9	113.4 (2)
C6—O1—C2	109.9 (2)	N3—C7—H7A	108.9
O1—C2—N3	111.3 (2)	C9—C7—H7A	108.9
O1—C2—H2A	109.4	N3—C7—H7B	108.9
N3—C2—H2A	109.4	C9—C7—H7B	108.9
O1—C2—H2B	109.4	H7A—C7—H7B	107.7
N3—C2—H2B	109.4	N5—C8—H8A	109.5
H2A—C2—H2B	108.0	N5—C8—H8B	109.5
C4—N3—C2	122.6 (2)	H8A—C8—H8B	109.5
C4—N3—C7	119.5 (2)	N5—C8—H8C	109.5
C2—N3—C7	117.6 (2)	H8A—C8—H8C	109.5
O7—C4—N5	123.6 (2)	H8B—C8—H8C	109.5
O7—C4—N3	121.1 (2)	C12—C9—C7	128.7 (2)
N5—C4—N3	115.3 (2)	C12—C9—S1	108.5 (2)
C4—N5—C8	121.5 (3)	C7—C9—S1	122.7 (2)
C4—N5—C6	120.9 (2)	N11—C10—S1	117.1 (2)
C8—N5—C6	117.4 (3)	N11—C10—Cl1	123.4 (2)
O1—C6—N5	111.1 (2)	S1—C10—Cl1	119.52 (14)
O1—C6—H6A	109.4	C10—N11—C12	108.3 (2)
N5—C6—H6A	109.4	C9—C12—N11	117.6 (2)
O1—C6—H6B	109.4	C9—C12—H12	121.2
N5—C6—H6B	109.4	N11—C12—H12	121.2
H6A—C6—H6B	108.0

C6—O1—C2—N3	54.5 (3)	C4—N3—C7—C9	85.9 (3)
O1—C2—N3—C4	−20.9 (4)	C2—N3—C7—C9	−87.9 (3)
O1—C2—N3—C7	152.7 (2)	N3—C7—C9—C12	111.4 (3)
C2—N3—C4—O7	172.1 (3)	N3—C7—C9—S1	−66.6 (3)
C7—N3—C4—O7	−1.3 (4)	C10—S1—C9—C12	−0.2 (2)
C2—N3—C4—N5	−7.7 (4)	C10—S1—C9—C7	178.1 (2)
C7—N3—C4—N5	178.8 (2)	C9—S1—C10—N11	0.3 (2)
O7—C4—N5—C8	−2.7 (5)	C9—S1—C10—Cl1	−178.75 (16)
N3—C4—N5—C8	177.2 (3)	S1—C10—N11—C12	−0.2 (3)
O7—C4—N5—C6	−177.5 (3)	Cl1—C10—N11—C12	178.8 (2)
N3—C4—N5—C6	2.4 (4)	C7—C9—C12—N11	−178.0 (3)
C2—O1—C6—N5	−59.9 (4)	S1—C9—C12—N11	0.2 (4)
C4—N5—C6—O1	31.4 (4)	C10—N11—C12—C9	0.0 (4)
C8—N5—C6—O1	−143.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O7ⁱ	0.93	2.60	3.443 (3)	151

Symmetry code: (i) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₀ClN₃O₂S
M_r	247.70
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	4.6141 (2), 11.7335 (4), 20.1460 (8)
V (Å³)	1090.70 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.925, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22323, 2147, 1974
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.081, 1.07
No. of reflections	2147
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.16
Absolute structure	Flack (1983), 856 Friedel pairs
Absolute structure parameter	0.04 (9)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O7ⁱ	0.93	2.60	3.443 (3)	151

Symmetry code: (i) −x, y+1/2, −z+3/2.

Acknowledgements

RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003.

References

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