(Z)-N-{3-[(2-Chloro-1,3-thia­zol-5-yl)meth­yl]-1,3-thia­zolidin-2-yl­idene}cyanamide

Li, Y.-M.; Li, J.-Y.; Wang, Q.; Hao, A.-Y.; Sun, T.

doi:10.1107/S1600536811047404

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3303

https://doi.org/10.1107/S1600536811047404

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(Z)-N-{3-[(2-Chloro-1,3-thiazol-5-yl)methyl]-1,3-thiazolidin-2-ylidene}cyanamide

Yue-Ming Li,^a Jian-Ye Li,^b Qian Wang,^c Ai-You Hao ^a ^* and Tao Sun ^a

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China, ^bChemical Engineering Department, Weifang University of Science and Technology, Shouguang 262700, People's Republic of China, and ^cBeijing University of Chemical Technology, Beijing 100029, People's Republic of China
^*Correspondence e-mail: haoay@sdu.edu.cn

(Received 18 October 2011; accepted 9 November 2011; online 12 November 2011)

In the title compound, C₈H₇ClN₄S₂, the thiazole ring is essentially planar [r.m.s. deviation = 0.0011 (2) Å] and conformation of the thiazolidine ring is twisted on the C—C bond. The C=N bond has a Z configuration.

Related literature

The title compound was synthesized as an intermediate for the preparation of pesticides. For the biological activity of this class of compounds, see: Zhang et al. (2000 ); Kagabu et al. (2008 ). For the synthesis, see: Kozo et al. (1987 ); Zuo et al. (2008 ). For a related structure. see Li et al. (2010 ).

Experimental

Crystal data

C₈H₇ClN₄S₂
M_r = 258.75
Monoclinic, P 2₁ /n
a = 9.6331 (12) Å
b = 11.2657 (14) Å
c = 10.7675 (13) Å
β = 112.433 (2)°
V = 1080.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.71 mm⁻¹
T = 273 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.901, T_max = 0.932
6191 measured reflections
2440 independent reflections
2075 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.108
S = 0.98
2440 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811047404/lh5358sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S1600536811047404/lh5358Isup2.mol

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811047404/lh5358Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811047404/lh5358Isup4.cml

checkCIF report

Comment top

It is already known that certain cyanoimino-subsitituted heterocyclic compounds are useful as intermediates in the preparation of pesticides which have played a major role in eliminating insects such as aphids, leafhoppers and whiteflies (Kagabu et al., 2008; Zhang et al., 2000). The molecular structure of the title compound is shown in Fig. 1. The thiazole ring is essentially planar (r.m.s. deviations 0.0011 (2)Å) and the thiazolidine ring is is in a slight half-chair conformation. The C═N bond with a Z configuration has a bond length of 1.150 (4) Å, which is in agreement with that in a related structure (Li et al., 2010).

Related literature top

The title compound was synthesized as an intermediate for the preparation of pesticides. For the biological activity of this class of compounds, see: Zhang et al. (2000); Kagabu et al. (2008). For the synthesis, see: Kozo et al. (1987); Zuo et al. (2008). For a related structure. see Li et al. (2010).

Experimental top

The synthesis of the title compound follows the method of Kozo et al. (1987) and Zuo, et al. (2008). (Z)-2-(1,3-Thiazolidin-2-ylidene)cyanamide 12.7 g (0.1 mol) and potassium carbonate 41.4 g (0.3 mol) were dissolved in N,N-dimethylformamide (DMF) (75 ml), then 2-chloro-5-thiazolylmethyl chloride 17.4 g (0.102 mol) dissolved in DMF (40 ml) was added dropwise. The mixture was stirred for 0.5 h at room temperature and filtered. The filtrate was concentrated and further purified by column chromatography to obtain the title product (13.9 g) with a yield of 53.7% Colorless crystals were obtained by slow evaporation of a tetrahydrofuran solution of the title compound at room temperature.

¹H NMR (300 MHz, DMSO-d6): δ (p.p.m.) 7.71 (1H, s), 4.79 (2H, s), 3.92 (2H, t, J = 15.3 Hz, J = 7.65 Hz); 3.49 (2H, t, J = 15.3 Hz, J = 7.65 Hz).

Structure description top

The title compound was synthesized as an intermediate for the preparation of pesticides. For the biological activity of this class of compounds, see: Zhang et al. (2000); Kagabu et al. (2008). For the synthesis, see: Kozo et al. (1987); Zuo et al. (2008). For a related structure. see Li et al. (2010).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at the 40% probability level.

(Z)-N-{3-[(2-Chloro-1,3-thiazol-5-yl)methyl]-1,3-thiazolidin-2- ylidene}cyanamide top

Crystal data top

C₈H₇ClN₄S₂	F(000) = 528
M_r = 258.75	D_x = 1.591 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3349 reflections
a = 9.6331 (12) Å	θ = 2.7–27.5°
b = 11.2657 (14) Å	µ = 0.71 mm⁻¹
c = 10.7675 (13) Å	T = 273 K
β = 112.433 (2)°	Block, colorless
V = 1080.1 (2) Å³	0.15 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2440 independent reflections
Radiation source: fine-focus sealed tube	2075 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
φ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.901, T_max = 0.932	k = −11→14
6191 measured reflections	l = −13→13

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0632P)² + 0.5077P] where P = (F_o² + 2F_c²)/3
2440 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₇ClN₄S₂	V = 1080.1 (2) Å³
M_r = 258.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6331 (12) Å	µ = 0.71 mm⁻¹
b = 11.2657 (14) Å	T = 273 K
c = 10.7675 (13) Å	0.15 × 0.10 × 0.10 mm
β = 112.433 (2)°

Data collection top

Bruker SMART CCD diffractometer	2440 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2075 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.932	R_int = 0.015
6191 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 0.98	Δρ_max = 0.38 e Å⁻³
2440 reflections	Δρ_min = −0.27 e Å⁻³
136 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.22859 (6)	0.11411 (5)	0.45559 (5)	0.04850 (16)
S2	0.42112 (6)	0.16077 (5)	0.07049 (5)	0.04881 (17)
Cl1	0.30959 (8)	0.27500 (7)	−0.19805 (6)	0.0715 (2)
N1	0.3166 (2)	−0.00659 (14)	0.29672 (16)	0.0445 (4)
C4	0.3566 (2)	0.02118 (18)	0.08619 (19)	0.0452 (4)
C2	0.3576 (2)	0.08458 (16)	0.38105 (18)	0.0398 (4)
C3	0.4033 (3)	−0.0430 (2)	0.2174 (2)	0.0532 (5)
H3A	0.3906	−0.1277	0.2004	0.064*
H3B	0.5090	−0.0282	0.2688	0.064*
C1	0.1211 (3)	−0.0170 (2)	0.3809 (3)	0.0680 (7)
H1A	0.1433	−0.0804	0.4466	0.082*
H1B	0.0144	0.0000	0.3481	0.082*
N2	0.4818 (2)	0.14397 (16)	0.40261 (18)	0.0485 (4)
C6	0.3112 (2)	0.1563 (2)	−0.09762 (19)	0.0475 (5)
N3	0.2328 (2)	0.0626 (2)	−0.14132 (17)	0.0598 (5)
C8	0.5191 (2)	0.22657 (19)	0.4975 (2)	0.0484 (5)
N4	0.5597 (3)	0.29942 (19)	0.5786 (2)	0.0680 (6)
C7	0.1657 (3)	−0.05279 (19)	0.2663 (2)	0.0527 (5)
H7A	0.1649	−0.1385	0.2579	0.063*
H7B	0.0961	−0.0197	0.1824	0.063*
C5	0.2592 (3)	−0.0145 (2)	−0.0353 (2)	0.0580 (6)
H5A	0.2118	−0.0880	−0.0471	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0521 (3)	0.0483 (3)	0.0467 (3)	0.0000 (2)	0.0207 (2)	−0.0068 (2)
S2	0.0445 (3)	0.0554 (3)	0.0384 (3)	−0.0010 (2)	0.0067 (2)	−0.0027 (2)
Cl1	0.0720 (4)	0.0877 (5)	0.0533 (3)	0.0002 (3)	0.0224 (3)	0.0209 (3)
N1	0.0568 (10)	0.0397 (8)	0.0339 (7)	0.0054 (7)	0.0139 (7)	−0.0003 (6)
C4	0.0520 (11)	0.0470 (10)	0.0371 (9)	0.0097 (8)	0.0176 (8)	−0.0041 (8)
C2	0.0474 (10)	0.0364 (9)	0.0315 (8)	0.0081 (7)	0.0104 (7)	0.0059 (7)
C3	0.0686 (14)	0.0465 (11)	0.0433 (10)	0.0187 (10)	0.0200 (10)	0.0000 (9)
C1	0.0731 (16)	0.0668 (15)	0.0673 (15)	−0.0213 (13)	0.0304 (13)	−0.0164 (12)
N2	0.0487 (9)	0.0484 (9)	0.0476 (9)	0.0013 (7)	0.0174 (8)	0.0004 (8)
C6	0.0418 (10)	0.0644 (13)	0.0353 (9)	0.0028 (9)	0.0137 (8)	0.0014 (9)
N3	0.0615 (11)	0.0772 (13)	0.0347 (8)	−0.0110 (10)	0.0114 (8)	−0.0067 (9)
C8	0.0432 (10)	0.0453 (11)	0.0526 (11)	−0.0015 (8)	0.0139 (9)	0.0059 (9)
N4	0.0686 (13)	0.0557 (12)	0.0721 (13)	−0.0149 (10)	0.0185 (11)	−0.0115 (10)
C7	0.0626 (13)	0.0431 (10)	0.0436 (10)	−0.0065 (9)	0.0105 (9)	−0.0029 (9)
C5	0.0721 (14)	0.0561 (13)	0.0446 (11)	−0.0100 (11)	0.0210 (10)	−0.0122 (10)

Geometric parameters (Å, º) top

S1—C2	1.749 (2)	C3—H3B	0.9700
S1—C1	1.807 (2)	C1—C7	1.508 (3)
S2—C6	1.714 (2)	C1—H1A	0.9700
S2—C4	1.723 (2)	C1—H1B	0.9700
Cl1—C6	1.716 (2)	N2—C8	1.326 (3)
N1—C2	1.327 (2)	C6—N3	1.279 (3)
N1—C7	1.459 (3)	N3—C5	1.378 (3)
N1—C3	1.463 (3)	C8—N4	1.153 (3)
C4—C5	1.348 (3)	C7—H7A	0.9700
C4—C3	1.495 (3)	C7—H7B	0.9700
C2—N2	1.313 (3)	C5—H5A	0.9300
C3—H3A	0.9700

C2—S1—C1	91.54 (11)	S1—C1—H1A	110.4
C6—S2—C4	88.65 (10)	C7—C1—H1B	110.4
C2—N1—C7	116.13 (17)	S1—C1—H1B	110.4
C2—N1—C3	121.99 (18)	H1A—C1—H1B	108.6
C7—N1—C3	120.70 (17)	C2—N2—C8	117.03 (18)
C5—C4—C3	128.3 (2)	N3—C6—S2	116.92 (17)
C5—C4—S2	108.70 (17)	N3—C6—Cl1	123.34 (16)
C3—C4—S2	123.00 (16)	S2—C6—Cl1	119.75 (13)
N2—C2—N1	121.90 (18)	C6—N3—C5	108.62 (18)
N2—C2—S1	125.56 (15)	N4—C8—N2	175.7 (2)
N1—C2—S1	112.54 (15)	N1—C7—C1	106.93 (17)
N1—C3—C4	112.53 (17)	N1—C7—H7A	110.3
N1—C3—H3A	109.1	C1—C7—H7A	110.3
C4—C3—H3A	109.1	N1—C7—H7B	110.3
N1—C3—H3B	109.1	C1—C7—H7B	110.3
C4—C3—H3B	109.1	H7A—C7—H7B	108.6
H3A—C3—H3B	107.8	C4—C5—N3	117.1 (2)
C7—C1—S1	106.81 (17)	C4—C5—H5A	121.4
C7—C1—H1A	110.4	N3—C5—H5A	121.4

C6—S2—C4—C5	−0.26 (17)	N1—C2—N2—C8	−174.14 (18)
C6—S2—C4—C3	−178.81 (18)	S1—C2—N2—C8	6.2 (3)
C7—N1—C2—N2	−170.80 (17)	C4—S2—C6—N3	0.15 (19)
C3—N1—C2—N2	−3.1 (3)	C4—S2—C6—Cl1	179.78 (14)
C7—N1—C2—S1	8.9 (2)	S2—C6—N3—C5	0.0 (3)
C3—N1—C2—S1	176.56 (14)	Cl1—C6—N3—C5	−179.61 (17)
C1—S1—C2—N2	−174.02 (19)	C2—N1—C7—C1	−22.8 (2)
C1—S1—C2—N1	6.31 (16)	C3—N1—C7—C1	169.36 (19)
C2—N1—C3—C4	−88.0 (2)	S1—C1—C7—N1	25.2 (2)
C7—N1—C3—C4	79.1 (2)	C3—C4—C5—N3	178.8 (2)
C5—C4—C3—N1	−95.7 (3)	S2—C4—C5—N3	0.3 (3)
S2—C4—C3—N1	82.6 (2)	C6—N3—C5—C4	−0.2 (3)
C2—S1—C1—C7	−18.40 (19)

Experimental details

Crystal data
Chemical formula	C₈H₇ClN₄S₂
M_r	258.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	273
a, b, c (Å)	9.6331 (12), 11.2657 (14), 10.7675 (13)
β (°)	112.433 (2)
V (Å³)	1080.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.71
Crystal size (mm)	0.15 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.901, 0.932
No. of measured, independent and observed [I > 2σ(I)] reflections	6191, 2440, 2075
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.108, 0.98
No. of reflections	2440
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.27

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (1998). SMART and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kagabu, S., Nishimura, K., Naruse, Y. & Ohno, I. (2008). J. Pestic. Sci. 33, 58–66. Web of Science CrossRef CAS Google Scholar
Kozo, S., Shinichi, T., Shinzo, K., Shoko, S., Koichi, M. & Yumi, H. (1987). EP Patent 235725. Google Scholar
Li, H., Zhang, X. & Xu, L. (2010). Acta Cryst. E66, o2171. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, A. G., Kayser, H., Maiensch, P. & Casida, J. E. (2000). J. Neurochem. 75, 1294–1303. Web of Science CrossRef PubMed CAS Google Scholar
Zuo, B. J., Shi, L. P., Li, L., Li, X. K. & Zhuang, Z. X. (2008). CN Patent 101250165. Google Scholar

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