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Acta Cryst. (2011). E67, o1140    [ doi:10.1107/S1600536811013316 ]

(Z)-N-{3-[(6-Chloropyridin-3-yl)methyl]-1,3-thiazolidin-2-ylidene}cyanamide

J.-S. Gao, J. Qiao, Y.-H. Yu and G.-F. Hou

Abstract top

The asymmetric unit of the title compound, C10H9ClN4S, common name thiacloprid, comprises two molecules. In both molecules, the thiazolidine 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-chloropyridine rings. In the crystal, intermolecular C-H...N hydrogen bonds links the molecules into chains propagating in [\overline101].

Comment top

Thiacloprid is the common name of the title compound, which is neonicotinoide class of insecticide. High efficacy and flexible application methods make it well suited for modern integrated pest management programs in many cropping systems (Ishimitsu et al., 1991; Maienfisch et al., 2003). We report here the synthesis and crystal structure of thiacloprid.

The asymmetric unit comprises two molecules; the thiazolidine rings are almost planar, and form the dihedral angles with 2-chloropyridine rings of 73.36 (6) and 70.25 (8)°, respectively (Fig. 1).

In the crystal, the intermolecular C—H···N hydrogen bonds link the molecules to form a chain (Fig. 2, Table 1).

Related literature top

For background of 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 top

The title compound was synthesised according the reference (Ishimitsu et al., 1991). A mixture of 2-cyanoiminothiazolidine (12.7 g, 0.1 mol), 2-chloro-5-pyridylmethyl-chloride (17.4 g, 0.1 mol), and K2CO3 (41.4 g, 0.3 mol) in 150 mL of DMF was heated to 323 K and kept stirring for 7 h. After filtered under reduced pressure, the DMF solution was distilled off. A total of 20.2 g (80.2%) title compound was obtained after the recrystallisation from ethyl acetate (15 mL). The suitable colourless block crystal was picked out for the single crystal X-ray diffaction measurement.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic); C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at the 50% probability level for non-H atoms.
[Figure 2] Fig. 2. A partial packing view, showing the hydrogen bonding chain. Dashed lines indicate the hydrogen bonds, no involving H atoms have been omitted for clarity.
(Z)-N-{3-[(6-Chloropyridin-3-yl)methyl]- 1,3-thiazolidin-2-ylidene}cyanamide top
Crystal data top
C10H9ClN4SF(000) = 1040
Mr = 252.73Dx = 1.486 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12991 reflections
a = 7.1294 (14) Åθ = 3.1–27.5°
b = 35.469 (7) ŵ = 0.50 mm−1
c = 9.0211 (18) ÅT = 293 K
β = 97.80 (3)°Block, colourless
V = 2260.1 (8) Å30.31 × 0.29 × 0.20 mm
Z = 8
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5151 independent reflections
Radiation source: fine-focus sealed tube3505 reflections with I > 2σ(I)
graphiteRint = 0.046
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −8→9
Tmin = 0.863, Tmax = 0.909k = −45→45
21869 measured reflectionsl = −11→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-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 parametersΔρmax = 0.21 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C10H9ClN4SV = 2260.1 (8) Å3
Mr = 252.73Z = 8
Monoclinic, P21/cMo Kα radiation
a = 7.1294 (14) ŵ = 0.50 mm−1
b = 35.469 (7) ÅT = 293 K
c = 9.0211 (18) Å0.31 × 0.29 × 0.20 mm
β = 97.80 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5151 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3505 reflections with I > 2σ(I)
Tmin = 0.863, Tmax = 0.909Rint = 0.046
21869 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.137Δρmax = 0.21 e Å−3
S = 1.08Δρmin = −0.29 e Å−3
5151 reflectionsAbsolute structure: ?
289 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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
xyzUiso*/Ueq
C10.8652 (3)0.04805 (6)0.2994 (3)0.0528 (6)
C20.7778 (4)0.05431 (7)0.4241 (3)0.0564 (6)
H20.83150.04610.51830.068*
C30.6087 (4)0.07309 (7)0.4038 (3)0.0541 (6)
H30.54430.07770.48500.065*
C40.5334 (3)0.08520 (5)0.2624 (3)0.0417 (5)
C50.6313 (4)0.07628 (6)0.1459 (3)0.0525 (6)
H50.57950.08350.05000.063*
C60.3545 (3)0.10860 (6)0.2362 (3)0.0486 (5)
H6A0.28560.10250.13900.058*
H6B0.27440.10240.31150.058*
C70.4452 (4)0.16785 (7)0.3852 (3)0.0586 (6)
H7A0.56770.15920.43310.070*
H7B0.35160.16220.45070.070*
C80.4506 (6)0.20899 (8)0.3572 (4)0.0831 (10)
H8A0.55730.22020.42000.100*
H8B0.33540.22070.38110.100*
C90.4189 (3)0.16902 (6)0.1222 (3)0.0422 (5)
C100.4177 (3)0.17589 (7)−0.1287 (3)0.0545 (6)
C111.3337 (3)0.05498 (7)0.7709 (3)0.0558 (6)
C121.2138 (4)0.04665 (8)0.8736 (3)0.0618 (6)
H121.23870.02680.94060.074*
C131.0549 (4)0.06898 (8)0.8737 (3)0.0609 (7)
H130.97120.06460.94230.073*
C141.0214 (3)0.09783 (7)0.7712 (3)0.0523 (6)
C151.1509 (4)0.10300 (8)0.6735 (3)0.0665 (7)
H151.12800.12220.60330.080*
C160.8483 (3)0.12283 (9)0.7672 (4)0.0678 (8)
H16A0.78180.12340.66600.081*
H16B0.76360.11210.83150.081*
C170.8939 (5)0.19245 (10)0.7102 (4)0.0840 (10)
H17A0.76640.19630.65950.101*
H17B0.97530.18660.63530.101*
C180.9605 (6)0.22673 (9)0.7904 (4)0.0853 (10)
H18A0.87990.24780.75560.102*
H18B1.08870.23250.77280.102*
C190.9155 (3)0.17075 (7)0.9595 (3)0.0464 (5)
C200.9267 (3)0.15741 (8)1.2059 (3)0.0593 (6)
Cl11.08715 (10)0.02601 (2)0.31970 (11)0.0811 (3)
Cl21.53924 (11)0.02813 (2)0.76846 (10)0.0809 (2)
N10.7967 (3)0.05776 (6)0.1620 (3)0.0592 (5)
N20.3963 (2)0.14899 (5)0.2425 (2)0.0432 (4)
N30.4000 (3)0.15412 (5)−0.0121 (2)0.0504 (5)
N40.4288 (4)0.19221 (7)−0.2375 (3)0.0777 (7)
N51.3080 (3)0.08234 (7)0.6720 (3)0.0658 (6)
N60.8957 (3)0.16118 (6)0.8155 (2)0.0540 (5)
N70.9051 (3)0.14604 (6)1.0652 (2)0.0551 (5)
N80.9439 (4)0.16423 (9)1.3319 (3)0.0864 (8)
S10.47264 (10)0.216369 (16)0.16494 (8)0.05802 (19)
S20.95422 (12)0.21907 (2)0.98475 (9)0.0698 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0496 (12)0.0361 (10)0.0750 (18)0.0031 (10)0.0159 (12)0.0066 (11)
C20.0653 (14)0.0536 (13)0.0499 (15)0.0087 (12)0.0069 (12)0.0066 (11)
C30.0656 (14)0.0505 (12)0.0483 (14)0.0063 (11)0.0159 (11)0.0021 (11)
C40.0476 (11)0.0336 (9)0.0458 (13)−0.0015 (9)0.0138 (9)0.0020 (8)
C50.0664 (14)0.0486 (12)0.0450 (14)0.0081 (11)0.0160 (11)0.0053 (10)
C60.0465 (11)0.0424 (11)0.0580 (15)−0.0045 (9)0.0113 (10)0.0002 (10)
C70.0753 (16)0.0539 (13)0.0462 (14)−0.0019 (12)0.0061 (12)−0.0049 (11)
C80.133 (3)0.0574 (16)0.060 (2)0.0008 (18)0.0185 (19)−0.0117 (14)
C90.0367 (10)0.0416 (10)0.0476 (13)0.0033 (8)0.0029 (9)0.0007 (9)
C100.0555 (13)0.0566 (13)0.0501 (15)0.0046 (11)0.0032 (11)0.0001 (12)
C110.0568 (13)0.0556 (13)0.0579 (16)−0.0027 (11)0.0177 (12)−0.0152 (12)
C120.0708 (16)0.0605 (15)0.0575 (17)−0.0074 (13)0.0214 (13)−0.0025 (12)
C130.0601 (14)0.0736 (16)0.0541 (16)−0.0178 (13)0.0257 (12)−0.0177 (13)
C140.0495 (12)0.0619 (14)0.0465 (14)−0.0090 (11)0.0106 (10)−0.0205 (11)
C150.0728 (17)0.0727 (17)0.0591 (18)0.0088 (14)0.0279 (14)0.0006 (13)
C160.0482 (13)0.0861 (19)0.0685 (19)−0.0033 (13)0.0062 (12)−0.0297 (15)
C170.096 (2)0.112 (3)0.0459 (17)0.009 (2)0.0141 (15)0.0145 (17)
C180.106 (2)0.0733 (19)0.080 (2)0.0222 (18)0.0239 (19)0.0220 (17)
C190.0389 (10)0.0567 (13)0.0438 (13)0.0051 (10)0.0068 (9)−0.0056 (10)
C200.0484 (12)0.0786 (17)0.0525 (16)0.0114 (12)0.0125 (11)0.0098 (13)
Cl10.0568 (4)0.0582 (4)0.1311 (8)0.0141 (3)0.0232 (4)0.0113 (4)
Cl20.0785 (5)0.0756 (5)0.0938 (6)0.0180 (4)0.0307 (4)−0.0044 (4)
N10.0684 (13)0.0531 (11)0.0623 (15)0.0100 (10)0.0310 (11)0.0084 (10)
N20.0454 (9)0.0407 (9)0.0437 (11)0.0020 (8)0.0068 (8)−0.0008 (8)
N30.0559 (11)0.0496 (10)0.0450 (12)0.0029 (9)0.0045 (9)−0.0002 (9)
N40.0968 (18)0.0831 (17)0.0537 (15)0.0063 (14)0.0119 (13)0.0126 (13)
N50.0701 (14)0.0680 (13)0.0662 (15)0.0064 (11)0.0349 (12)−0.0018 (11)
N60.0504 (10)0.0702 (13)0.0413 (11)0.0095 (10)0.0058 (8)−0.0082 (9)
N70.0581 (11)0.0601 (12)0.0485 (13)0.0040 (10)0.0129 (9)0.0025 (9)
N80.0813 (17)0.133 (2)0.0470 (15)0.0174 (16)0.0147 (12)0.0044 (15)
S10.0681 (4)0.0420 (3)0.0615 (4)−0.0052 (3)−0.0003 (3)0.0019 (3)
S20.0892 (5)0.0566 (4)0.0649 (5)0.0004 (3)0.0145 (4)−0.0053 (3)
Geometric parameters (Å, °) top
C1—N11.314 (3)C11—N51.314 (4)
C1—C21.376 (4)C11—C121.375 (4)
C1—Cl11.752 (2)C11—Cl21.750 (3)
C2—C31.368 (3)C12—C131.383 (4)
C2—H20.9300C12—H120.9300
C3—C41.383 (3)C13—C141.378 (4)
C3—H30.9300C13—H130.9300
C4—C51.375 (3)C14—C151.373 (4)
C4—C61.513 (3)C14—C161.516 (4)
C5—N11.340 (3)C15—N51.340 (4)
C5—H50.9300C15—H150.9300
C6—N21.463 (3)C16—N61.454 (3)
C6—H6A0.9700C16—H16A0.9700
C6—H6B0.9700C16—H16B0.9700
C7—N21.451 (3)C17—N61.459 (4)
C7—C81.482 (4)C17—C181.461 (5)
C7—H7A0.9700C17—H17A0.9700
C7—H7B0.9700C17—H17B0.9700
C8—S11.782 (3)C18—S21.781 (4)
C8—H8A0.9700C18—H18A0.9700
C8—H8B0.9700C18—H18B0.9700
C9—N31.312 (3)C19—N71.305 (3)
C9—N21.325 (3)C19—N61.331 (3)
C9—S11.754 (2)C19—S21.746 (2)
C10—N41.152 (3)C20—N81.152 (4)
C10—N31.324 (3)C20—N71.321 (3)
N1—C1—C2125.2 (2)C14—C13—C12119.5 (2)
N1—C1—Cl1115.5 (2)C14—C13—H13120.2
C2—C1—Cl1119.3 (2)C12—C13—H13120.2
C3—C2—C1117.2 (2)C15—C14—C13117.3 (2)
C3—C2—H2121.4C15—C14—C16121.5 (3)
C1—C2—H2121.4C13—C14—C16121.1 (3)
C2—C3—C4120.0 (2)N5—C15—C14124.7 (3)
C2—C3—H3120.0N5—C15—H15117.6
C4—C3—H3120.0C14—C15—H15117.6
C5—C4—C3117.4 (2)N6—C16—C14112.62 (19)
C5—C4—C6120.7 (2)N6—C16—H16A109.1
C3—C4—C6121.9 (2)C14—C16—H16A109.1
N1—C5—C4124.1 (2)N6—C16—H16B109.1
N1—C5—H5118.0C14—C16—H16B109.1
C4—C5—H5118.0H16A—C16—H16B107.8
N2—C6—C4111.60 (17)N6—C17—C18109.7 (3)
N2—C6—H6A109.3N6—C17—H17A109.7
C4—C6—H6A109.3C18—C17—H17A109.7
N2—C6—H6B109.3N6—C17—H17B109.7
C4—C6—H6B109.3C18—C17—H17B109.7
H6A—C6—H6B108.0H17A—C17—H17B108.2
N2—C7—C8108.2 (2)C17—C18—S2108.1 (2)
N2—C7—H7A110.1C17—C18—H18A110.1
C8—C7—H7A110.1S2—C18—H18A110.1
N2—C7—H7B110.1C17—C18—H18B110.1
C8—C7—H7B110.1S2—C18—H18B110.1
H7A—C7—H7B108.4H18A—C18—H18B108.4
C7—C8—S1108.5 (2)N7—C19—N6122.2 (2)
C7—C8—H8A110.0N7—C19—S2125.99 (19)
S1—C8—H8A110.0N6—C19—S2111.81 (18)
C7—C8—H8B110.0N8—C20—N7174.3 (3)
S1—C8—H8B110.0C1—N1—C5116.1 (2)
H8A—C8—H8B108.4C9—N2—C7116.01 (19)
N3—C9—N2122.1 (2)C9—N2—C6122.68 (19)
N3—C9—S1125.52 (18)C7—N2—C6120.61 (19)
N2—C9—S1112.34 (17)C9—N3—C10119.3 (2)
N4—C10—N3174.2 (3)C11—N5—C15115.9 (2)
N5—C11—C12125.0 (2)C19—N6—C16121.3 (2)
N5—C11—Cl2115.7 (2)C19—N6—C17115.6 (2)
C12—C11—Cl2119.3 (2)C16—N6—C17122.3 (2)
C11—C12—C13117.5 (3)C19—N7—C20119.1 (2)
C11—C12—H12121.3C9—S1—C891.61 (12)
C13—C12—H12121.3C19—S2—C1892.62 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N5i0.932.553.459 (4)167
C13—H13···N1ii0.932.493.408 (4)169
Symmetry codes: (i) x−1, y, z; (ii) x, y, z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N5i0.932.553.459 (4)167
C13—H13···N1ii0.932.493.408 (4)169
Symmetry codes: (i) x−1, y, z; (ii) x, y, z+1.
Acknowledgements top

The authors thank the Special Funds for the Research of Scientific and Technological Innovative Talents of Harbin Municipal Science and Technology Bureau (2009RFXXG027), the Science and Technology Planning Project of Heilongjiang Province (GZ08A401) and Heilongjiang University for supporting this study.

references
References top

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Ishimitsu, K., Suzuki, J., Ohishi, H., Yamada, T., Hatano, R., Takakusa, N. & Mitsui, J. (1991). WO Patent 91/04965.

Maienfisch, P., Haettenschwiler, J., Rindlisbacher, A., Decock, A., Wellmann, H. & Kayser, H. (2003). Chimia, 57, 710–714.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.