(Z)-N-{3-[(6-Chloro-pyridin-3-yl)meth-yl]-1,3-thia-zolidin-2-yl-idene}cyanamide.

The asymmetric unit of the title compound, C(10)H(9)ClN(4)S, common name thia-cloprid, comprises two mol-ecules. In both mol-ecules, the thia-zolidine rings are almost planar (with r.m.s. deviations of 0.016 and 0.065 Å) and form dihedral angles of 73.36 (6) and 70.25 (8)° with the 2-chloro-pyridine rings. In the crystal, inter-molecular C-H⋯N hydrogen bonds links the mol-ecules into chains propagating in [[Formula: see text]01].

Related literature

For background to the title compound, a member of the neonicotinoide class of insecticides, see Maienfisch et al. (2003 ▶). For the synthesis, see Ishimitsu et al., (1991 ▶)

Experimental

Crystal data

C10H9ClN4S

M = 252.73

Monoclinic,

a = 7.1294 (14) Å

b = 35.469 (7) Å

c = 9.0211 (18) Å

β = 97.80 (3)°

V = 2260.1 (8) Å3

Z = 8

Mo Kα radiation

μ = 0.50 mm−1

T = 293 K

0.31 × 0.29 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.863, T max = 0.909

21869 measured reflections

5151 independent reflections

3505 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.137

S = 1.08

5151 reflections

289 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.29 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811013316/kp2319sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013316/kp2319Isup2.hkl

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

C10H9ClN4S	F(000) = 1040
Mr = 252.73	Dx = 1.486 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12991 reflections
a = 7.1294 (14) Å	θ = 3.1–27.5°
b = 35.469 (7) Å	µ = 0.50 mm−1
c = 9.0211 (18) Å	T = 293 K
β = 97.80 (3)°	Block, colourless
V = 2260.1 (8) Å3	0.31 × 0.29 × 0.20 mm
Z = 8

Rigaku R-AXIS RAPID diffractometer	5151 independent reflections
Radiation source: fine-focus sealed tube	3505 reflections with I > 2σ(I)
graphite	Rint = 0.046
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
Tmin = 0.863, Tmax = 0.909	k = −45→45
21869 measured reflections	l = −11→11

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0595P)2 + 0.4995P] where P = (Fo2 + 2Fc2)/3
5151 reflections	(Δ/σ)max < 0.001
289 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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
C1	0.8652 (3)	0.04805 (6)	0.2994 (3)	0.0528 (6)
C2	0.7778 (4)	0.05431 (7)	0.4241 (3)	0.0564 (6)
H2	0.8315	0.0461	0.5183	0.068*
C3	0.6087 (4)	0.07309 (7)	0.4038 (3)	0.0541 (6)
H3	0.5443	0.0777	0.4850	0.065*
C4	0.5334 (3)	0.08520 (5)	0.2624 (3)	0.0417 (5)
C5	0.6313 (4)	0.07628 (6)	0.1459 (3)	0.0525 (6)
H5	0.5795	0.0835	0.0500	0.063*
C6	0.3545 (3)	0.10860 (6)	0.2362 (3)	0.0486 (5)
H6A	0.2856	0.1025	0.1390	0.058*
H6B	0.2744	0.1024	0.3115	0.058*
C7	0.4452 (4)	0.16785 (7)	0.3852 (3)	0.0586 (6)
H7A	0.5677	0.1592	0.4331	0.070*
H7B	0.3516	0.1622	0.4507	0.070*
C8	0.4506 (6)	0.20899 (8)	0.3572 (4)	0.0831 (10)
H8A	0.5573	0.2202	0.4200	0.100*
H8B	0.3354	0.2207	0.3811	0.100*
C9	0.4189 (3)	0.16902 (6)	0.1222 (3)	0.0422 (5)
C10	0.4177 (3)	0.17589 (7)	−0.1287 (3)	0.0545 (6)
C11	1.3337 (3)	0.05498 (7)	0.7709 (3)	0.0558 (6)
C12	1.2138 (4)	0.04665 (8)	0.8736 (3)	0.0618 (6)
H12	1.2387	0.0268	0.9406	0.074*
C13	1.0549 (4)	0.06898 (8)	0.8737 (3)	0.0609 (7)
H13	0.9712	0.0646	0.9423	0.073*
C14	1.0214 (3)	0.09783 (7)	0.7712 (3)	0.0523 (6)
C15	1.1509 (4)	0.10300 (8)	0.6735 (3)	0.0665 (7)
H15	1.1280	0.1222	0.6033	0.080*
C16	0.8483 (3)	0.12283 (9)	0.7672 (4)	0.0678 (8)
H16A	0.7818	0.1234	0.6660	0.081*
H16B	0.7636	0.1121	0.8315	0.081*
C17	0.8939 (5)	0.19245 (10)	0.7102 (4)	0.0840 (10)
H17A	0.7664	0.1963	0.6595	0.101*
H17B	0.9753	0.1866	0.6353	0.101*
C18	0.9605 (6)	0.22673 (9)	0.7904 (4)	0.0853 (10)
H18A	0.8799	0.2478	0.7556	0.102*
H18B	1.0887	0.2325	0.7728	0.102*
C19	0.9155 (3)	0.17075 (7)	0.9595 (3)	0.0464 (5)
C20	0.9267 (3)	0.15741 (8)	1.2059 (3)	0.0593 (6)
Cl1	1.08715 (10)	0.02601 (2)	0.31970 (11)	0.0811 (3)
Cl2	1.53924 (11)	0.02813 (2)	0.76846 (10)	0.0809 (2)
N1	0.7967 (3)	0.05776 (6)	0.1620 (3)	0.0592 (5)
N2	0.3963 (2)	0.14899 (5)	0.2425 (2)	0.0432 (4)
N3	0.4000 (3)	0.15412 (5)	−0.0121 (2)	0.0504 (5)
N4	0.4288 (4)	0.19221 (7)	−0.2375 (3)	0.0777 (7)
N5	1.3080 (3)	0.08234 (7)	0.6720 (3)	0.0658 (6)
N6	0.8957 (3)	0.16118 (6)	0.8155 (2)	0.0540 (5)
N7	0.9051 (3)	0.14604 (6)	1.0652 (2)	0.0551 (5)
N8	0.9439 (4)	0.16423 (9)	1.3319 (3)	0.0864 (8)
S1	0.47264 (10)	0.216369 (16)	0.16494 (8)	0.05802 (19)
S2	0.95422 (12)	0.21907 (2)	0.98475 (9)	0.0698 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0496 (12)	0.0361 (10)	0.0750 (18)	0.0031 (10)	0.0159 (12)	0.0066 (11)
C2	0.0653 (14)	0.0536 (13)	0.0499 (15)	0.0087 (12)	0.0069 (12)	0.0066 (11)
C3	0.0656 (14)	0.0505 (12)	0.0483 (14)	0.0063 (11)	0.0159 (11)	0.0021 (11)
C4	0.0476 (11)	0.0336 (9)	0.0458 (13)	−0.0015 (9)	0.0138 (9)	0.0020 (8)
C5	0.0664 (14)	0.0486 (12)	0.0450 (14)	0.0081 (11)	0.0160 (11)	0.0053 (10)
C6	0.0465 (11)	0.0424 (11)	0.0580 (15)	−0.0045 (9)	0.0113 (10)	0.0002 (10)
C7	0.0753 (16)	0.0539 (13)	0.0462 (14)	−0.0019 (12)	0.0061 (12)	−0.0049 (11)
C8	0.133 (3)	0.0574 (16)	0.060 (2)	0.0008 (18)	0.0185 (19)	−0.0117 (14)
C9	0.0367 (10)	0.0416 (10)	0.0476 (13)	0.0033 (8)	0.0029 (9)	0.0007 (9)
C10	0.0555 (13)	0.0566 (13)	0.0501 (15)	0.0046 (11)	0.0032 (11)	0.0001 (12)
C11	0.0568 (13)	0.0556 (13)	0.0579 (16)	−0.0027 (11)	0.0177 (12)	−0.0152 (12)
C12	0.0708 (16)	0.0605 (15)	0.0575 (17)	−0.0074 (13)	0.0214 (13)	−0.0025 (12)
C13	0.0601 (14)	0.0736 (16)	0.0541 (16)	−0.0178 (13)	0.0257 (12)	−0.0177 (13)
C14	0.0495 (12)	0.0619 (14)	0.0465 (14)	−0.0090 (11)	0.0106 (10)	−0.0205 (11)
C15	0.0728 (17)	0.0727 (17)	0.0591 (18)	0.0088 (14)	0.0279 (14)	0.0006 (13)
C16	0.0482 (13)	0.0861 (19)	0.0685 (19)	−0.0033 (13)	0.0062 (12)	−0.0297 (15)
C17	0.096 (2)	0.112 (3)	0.0459 (17)	0.009 (2)	0.0141 (15)	0.0145 (17)
C18	0.106 (2)	0.0733 (19)	0.080 (2)	0.0222 (18)	0.0239 (19)	0.0220 (17)
C19	0.0389 (10)	0.0567 (13)	0.0438 (13)	0.0051 (10)	0.0068 (9)	−0.0056 (10)
C20	0.0484 (12)	0.0786 (17)	0.0525 (16)	0.0114 (12)	0.0125 (11)	0.0098 (13)
Cl1	0.0568 (4)	0.0582 (4)	0.1311 (8)	0.0141 (3)	0.0232 (4)	0.0113 (4)
Cl2	0.0785 (5)	0.0756 (5)	0.0938 (6)	0.0180 (4)	0.0307 (4)	−0.0044 (4)
N1	0.0684 (13)	0.0531 (11)	0.0623 (15)	0.0100 (10)	0.0310 (11)	0.0084 (10)
N2	0.0454 (9)	0.0407 (9)	0.0437 (11)	0.0020 (8)	0.0068 (8)	−0.0008 (8)
N3	0.0559 (11)	0.0496 (10)	0.0450 (12)	0.0029 (9)	0.0045 (9)	−0.0002 (9)
N4	0.0968 (18)	0.0831 (17)	0.0537 (15)	0.0063 (14)	0.0119 (13)	0.0126 (13)
N5	0.0701 (14)	0.0680 (13)	0.0662 (15)	0.0064 (11)	0.0349 (12)	−0.0018 (11)
N6	0.0504 (10)	0.0702 (13)	0.0413 (11)	0.0095 (10)	0.0058 (8)	−0.0082 (9)
N7	0.0581 (11)	0.0601 (12)	0.0485 (13)	0.0040 (10)	0.0129 (9)	0.0025 (9)
N8	0.0813 (17)	0.133 (2)	0.0470 (15)	0.0174 (16)	0.0147 (12)	0.0044 (15)
S1	0.0681 (4)	0.0420 (3)	0.0615 (4)	−0.0052 (3)	−0.0003 (3)	0.0019 (3)
S2	0.0892 (5)	0.0566 (4)	0.0649 (5)	0.0004 (3)	0.0145 (4)	−0.0053 (3)

C1—N1	1.314 (3)	C11—N5	1.314 (4)
C1—C2	1.376 (4)	C11—C12	1.375 (4)
C1—Cl1	1.752 (2)	C11—Cl2	1.750 (3)
C2—C3	1.368 (3)	C12—C13	1.383 (4)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.383 (3)	C13—C14	1.378 (4)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.375 (3)	C14—C15	1.373 (4)
C4—C6	1.513 (3)	C14—C16	1.516 (4)
C5—N1	1.340 (3)	C15—N5	1.340 (4)
C5—H5	0.9300	C15—H15	0.9300
C6—N2	1.463 (3)	C16—N6	1.454 (3)
C6—H6A	0.9700	C16—H16A	0.9700
C6—H6B	0.9700	C16—H16B	0.9700
C7—N2	1.451 (3)	C17—N6	1.459 (4)
C7—C8	1.482 (4)	C17—C18	1.461 (5)
C7—H7A	0.9700	C17—H17A	0.9700
C7—H7B	0.9700	C17—H17B	0.9700
C8—S1	1.782 (3)	C18—S2	1.781 (4)
C8—H8A	0.9700	C18—H18A	0.9700
C8—H8B	0.9700	C18—H18B	0.9700
C9—N3	1.312 (3)	C19—N7	1.305 (3)
C9—N2	1.325 (3)	C19—N6	1.331 (3)
C9—S1	1.754 (2)	C19—S2	1.746 (2)
C10—N4	1.152 (3)	C20—N8	1.152 (4)
C10—N3	1.324 (3)	C20—N7	1.321 (3)
N1—C1—C2	125.2 (2)	C14—C13—C12	119.5 (2)
N1—C1—Cl1	115.5 (2)	C14—C13—H13	120.2
C2—C1—Cl1	119.3 (2)	C12—C13—H13	120.2
C3—C2—C1	117.2 (2)	C15—C14—C13	117.3 (2)
C3—C2—H2	121.4	C15—C14—C16	121.5 (3)
C1—C2—H2	121.4	C13—C14—C16	121.1 (3)
C2—C3—C4	120.0 (2)	N5—C15—C14	124.7 (3)
C2—C3—H3	120.0	N5—C15—H15	117.6
C4—C3—H3	120.0	C14—C15—H15	117.6
C5—C4—C3	117.4 (2)	N6—C16—C14	112.62 (19)
C5—C4—C6	120.7 (2)	N6—C16—H16A	109.1
C3—C4—C6	121.9 (2)	C14—C16—H16A	109.1
N1—C5—C4	124.1 (2)	N6—C16—H16B	109.1
N1—C5—H5	118.0	C14—C16—H16B	109.1
C4—C5—H5	118.0	H16A—C16—H16B	107.8
N2—C6—C4	111.60 (17)	N6—C17—C18	109.7 (3)
N2—C6—H6A	109.3	N6—C17—H17A	109.7
C4—C6—H6A	109.3	C18—C17—H17A	109.7
N2—C6—H6B	109.3	N6—C17—H17B	109.7
C4—C6—H6B	109.3	C18—C17—H17B	109.7
H6A—C6—H6B	108.0	H17A—C17—H17B	108.2
N2—C7—C8	108.2 (2)	C17—C18—S2	108.1 (2)
N2—C7—H7A	110.1	C17—C18—H18A	110.1
C8—C7—H7A	110.1	S2—C18—H18A	110.1
N2—C7—H7B	110.1	C17—C18—H18B	110.1
C8—C7—H7B	110.1	S2—C18—H18B	110.1
H7A—C7—H7B	108.4	H18A—C18—H18B	108.4
C7—C8—S1	108.5 (2)	N7—C19—N6	122.2 (2)
C7—C8—H8A	110.0	N7—C19—S2	125.99 (19)
S1—C8—H8A	110.0	N6—C19—S2	111.81 (18)
C7—C8—H8B	110.0	N8—C20—N7	174.3 (3)
S1—C8—H8B	110.0	C1—N1—C5	116.1 (2)
H8A—C8—H8B	108.4	C9—N2—C7	116.01 (19)
N3—C9—N2	122.1 (2)	C9—N2—C6	122.68 (19)
N3—C9—S1	125.52 (18)	C7—N2—C6	120.61 (19)
N2—C9—S1	112.34 (17)	C9—N3—C10	119.3 (2)
N4—C10—N3	174.2 (3)	C11—N5—C15	115.9 (2)
N5—C11—C12	125.0 (2)	C19—N6—C16	121.3 (2)
N5—C11—Cl2	115.7 (2)	C19—N6—C17	115.6 (2)
C12—C11—Cl2	119.3 (2)	C16—N6—C17	122.3 (2)
C11—C12—C13	117.5 (3)	C19—N7—C20	119.1 (2)
C11—C12—H12	121.3	C9—S1—C8	91.61 (12)
C13—C12—H12	121.3	C19—S2—C18	92.62 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N5i	0.93	2.55	3.459 (4)	167
C13—H13···N1ii	0.93	2.49	3.408 (4)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N5i	0.93	2.55	3.459 (4)	167
C13—H13⋯N1ii	0.93	2.49	3.408 (4)	169

Symmetry codes: (i) ; (ii) .