(Z)-N-{3-[1-(4-Chloro­phen­yl)eth­yl]thia­zolidin-2-yl­idene}cyanamide

Li, H.; Zhang, X.; Xu, L.

doi:10.1107/S1600536810029879

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2171

https://doi.org/10.1107/S1600536810029879

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(Z)-N-{3-[1-(4-Chlorophenyl)ethyl]thiazolidin-2-ylidene}cyanamide

Hong-xin Li,^a Xiao-jun Zhang ^a and Liang-zhong Xu ^a ^*

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: nyhxpyjs@yahoo.com.cn

(Received 16 July 2010; accepted 27 July 2010; online 31 July 2010)

The title compound, C₁₂H₁₂ClN₃S, features a thiazolyl ring having an envelope conformation with the –CH₂– group bonded to the S atom forming the flap. The C=N double bond has a Z configuration. The crystal structure shows intermolecular C—H⋯S hydrogen bonds.

Related literature

For the biological activity of thiazole componds, see: Hense et al. (2002 ). For a related structure, see: Cunico et al. (2007 ). For the synthesis, see: Jeschke et al. (2002 ).

Experimental

Crystal data

C₁₂H₁₂ClN₃S
M_r = 265.76
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.8850 (12) Å
b = 7.5965 (15) Å
c = 28.273 (6) Å
V = 1264.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 113 K
0.14 × 0.12 × 0.10 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.940, T_max = 0.957
9219 measured reflections
3019 independent reflections
2640 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.113
S = 1.06
3019 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ), 6200 Friedel pairs
Flack parameter: −0.09 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯S1ⁱ	0.97	2.87	3.799 (4)	160
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536810029879/ng5002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029879/ng5002Isup2.hkl

checkCIF report

Comment top

Recently, compounds containing the 2-(thiazolidin-2-ylidene)malononitrile group have attracted much interest because its containing a thiazole ring system are well known as efficient insecticide in pesticides, and have good plant-growth regulatory activity for a wide variety of crops e.g. thiacloprid (Hense et al., 2002). A new compound, (I), which containing thiazole ring has higher insecticide activity. We report here the crystal structure and synthesis of (I).

In (I) (Fig. 1), the bond lengths and angles are normal and in a agreement with those common to a previously reported structure (Cunico, et al., 2007). The thiazole ring is in and envelope conformation with the –CH₂– group bonded to the S atom forming the flap. The carbon-nitrogen double bond of the molecule is trans. Flack x parameter = -0.0865 (with e.s.d. 0.0872) (Flack, 1983). The crystal structure involves C—H···S intermolecular hydrogen bonds.

Related literature top

For the biological activity of thiazole componds, see: Hense et al. (2002). For a related structure, see: Cunico, et al. (2007). For the synthesis, see: Jeschke et al. (2002).

Experimental top

(Z)-(thiazolidin-2-ylideneamino)formonitrile 1.27 g (10.0 mmol) and potassium carbonate (10.0 mmol) were dissolved in N,N-dimethylformamide(DMF) (15 ml) which was stirred 0.5 h at room temperature. Then 1-chloro-4-(1-chloroethyl)benzene 1.75 g (10.0 mmol) was added dropwising within 2 h at 283 K. The mixture was stirred for 8 h at 428 K. Upon cooling at room temperature. Then water (20 ml) was added. The mixture was extracted with CH₂Cl₂ (15 ml) and the organic layer was washed with water and dried over anhydrous sodium sulfate. The excess CH₂Cl₂ was removed on a water vacuum pump to obtain the oily product. Crystallized from methanol to afford the title compound 2.0 g (76% yield) (Jeschke, et al., 2002.). Single crystals suitable for X-ray measurement were obtained by recrystallization from the mixture of acetone and methanol at room temperature.

Structure description top

For the biological activity of thiazole componds, see: Hense et al. (2002). For a related structure, see: Cunico, et al. (2007). For the synthesis, see: Jeschke et al. (2002).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (I), with displacement ellipsoids drawn at the 40% probability level.

(Z)-N-{3-[1-(4-Chlorophenyl)ethyl]thiazolidin-2-ylidene}cyanamide top

Crystal data top

C₁₂H₁₂ClN₃S	F(000) = 552
M_r = 265.76	D_x = 1.397 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 193 reflections
a = 5.8850 (12) Å	θ = 1.4–27.9°
b = 7.5965 (15) Å	µ = 0.45 mm⁻¹
c = 28.273 (6) Å	T = 113 K
V = 1264.0 (4) Å³	Block, white
Z = 4	0.14 × 0.12 × 0.10 mm

Data collection top

Rigaku Saturn diffractometer	3019 independent reflections
Radiation source: rotating anode	2640 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.062
ω scans	θ_max = 27.9°, θ_min = 1.4°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −7→7
T_min = 0.940, T_max = 0.957	k = −9→8
9219 measured reflections	l = −29→37

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0534P)² + 0.0295P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3019 reflections	Δρ_max = 0.38 e Å⁻³
155 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 6200 Friedel pairs
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₂H₁₂ClN₃S	V = 1264.0 (4) Å³
M_r = 265.76	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.8850 (12) Å	µ = 0.45 mm⁻¹
b = 7.5965 (15) Å	T = 113 K
c = 28.273 (6) Å	0.14 × 0.12 × 0.10 mm

Data collection top

Rigaku Saturn diffractometer	3019 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2640 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.957	R_int = 0.062
9219 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.06	Δρ_max = 0.38 e Å⁻³
3019 reflections	Δρ_min = −0.34 e Å⁻³
155 parameters	Absolute structure: Flack (1983), 6200 Friedel pairs

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
Cl1	0.31420 (16)	−0.62970 (7)	0.98241 (2)	0.0438 (2)
S1	0.18444 (12)	0.16944 (8)	0.77090 (2)	0.03081 (17)
N2	0.2773 (4)	0.3380 (3)	0.85392 (7)	0.0279 (4)
C9	0.3024 (4)	0.1982 (3)	0.82718 (8)	0.0238 (5)
C1	0.2990 (4)	−0.1331 (3)	0.93777 (8)	0.0267 (5)
H1	0.2024	−0.0368	0.9407	0.032*
N1	0.4250 (4)	0.0594 (2)	0.84129 (6)	0.0255 (5)
C6	0.4992 (4)	−0.1158 (3)	0.91192 (8)	0.0242 (5)
C7	0.5466 (4)	0.0572 (3)	0.88698 (8)	0.0257 (5)
H7	0.4806	0.1507	0.9065	0.031*
C8	0.7950 (5)	0.1029 (4)	0.87970 (9)	0.0369 (6)
H8A	0.8064	0.2125	0.8630	0.055*
H8B	0.8672	0.0117	0.8616	0.055*
H8C	0.8686	0.1135	0.9099	0.055*
C12	0.1462 (5)	0.4672 (3)	0.83801 (8)	0.0294 (6)
C2	0.2409 (4)	−0.2905 (3)	0.95914 (8)	0.0288 (5)
H2	0.1055	−0.3011	0.9759	0.035*
C4	0.5886 (5)	−0.4192 (3)	0.93042 (9)	0.0316 (6)
H4	0.6860	−0.5152	0.9284	0.038*
C3	0.3874 (5)	−0.4315 (3)	0.95515 (8)	0.0285 (5)
N3	0.0347 (5)	0.5868 (3)	0.82737 (8)	0.0414 (6)
C5	0.6432 (5)	−0.2610 (3)	0.90865 (8)	0.0292 (6)
H5	0.7778	−0.2518	0.8916	0.035*
C11	0.4588 (7)	−0.0759 (4)	0.80600 (9)	0.0479 (8)
H11A	0.6166	−0.0769	0.7961	0.058*
H11B	0.4235	−0.1901	0.8195	0.058*
C10	0.3144 (8)	−0.0437 (4)	0.76555 (12)	0.0648 (12)
H10A	0.1977	−0.1336	0.7638	0.078*
H10B	0.4039	−0.0488	0.7368	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0702 (5)	0.0288 (3)	0.0324 (4)	−0.0048 (3)	0.0066 (4)	0.0021 (3)
S1	0.0384 (4)	0.0355 (3)	0.0185 (3)	−0.0011 (3)	−0.0028 (3)	0.0002 (2)
N2	0.0319 (11)	0.0266 (9)	0.0252 (11)	−0.0013 (9)	−0.0015 (9)	−0.0014 (8)
C9	0.0227 (11)	0.0302 (11)	0.0186 (11)	−0.0047 (10)	0.0030 (10)	0.0020 (8)
C1	0.0253 (12)	0.0304 (11)	0.0246 (12)	0.0062 (11)	0.0008 (10)	0.0000 (9)
N1	0.0305 (11)	0.0255 (10)	0.0204 (11)	0.0005 (9)	−0.0029 (9)	−0.0032 (8)
C6	0.0232 (11)	0.0293 (11)	0.0201 (12)	−0.0007 (9)	−0.0038 (9)	−0.0022 (9)
C7	0.0267 (12)	0.0289 (12)	0.0215 (13)	−0.0010 (10)	−0.0029 (10)	−0.0016 (9)
C8	0.0319 (14)	0.0419 (14)	0.0368 (16)	−0.0080 (13)	−0.0029 (12)	0.0067 (12)
C12	0.0371 (15)	0.0332 (12)	0.0179 (12)	−0.0011 (11)	0.0008 (10)	−0.0010 (9)
C2	0.0284 (13)	0.0332 (12)	0.0249 (13)	−0.0021 (10)	0.0014 (10)	−0.0010 (10)
C4	0.0376 (14)	0.0252 (11)	0.0319 (14)	0.0079 (11)	−0.0017 (11)	−0.0064 (10)
C3	0.0386 (14)	0.0260 (11)	0.0210 (13)	−0.0031 (11)	−0.0019 (10)	−0.0016 (10)
N3	0.0575 (17)	0.0394 (12)	0.0273 (13)	0.0087 (12)	−0.0025 (11)	−0.0006 (10)
C5	0.0296 (14)	0.0329 (11)	0.0252 (14)	0.0034 (11)	0.0024 (10)	−0.0026 (10)
C11	0.069 (2)	0.0489 (16)	0.0254 (15)	0.0203 (17)	−0.0048 (14)	−0.0132 (13)
C10	0.097 (3)	0.0508 (18)	0.046 (2)	0.027 (2)	−0.038 (2)	−0.0243 (14)

Geometric parameters (Å, º) top

Cl1—C3	1.746 (2)	C8—H8A	0.9600
S1—C9	1.750 (2)	C8—H8B	0.9600
S1—C10	1.797 (3)	C8—H8C	0.9600
N2—C9	1.311 (3)	C12—N3	1.161 (3)
N2—C12	1.327 (3)	C2—C3	1.380 (4)
C9—N1	1.338 (3)	C2—H2	0.9300
C1—C2	1.383 (3)	C4—C3	1.378 (4)
C1—C6	1.393 (3)	C4—C5	1.388 (3)
C1—H1	0.9300	C4—H4	0.9300
N1—C11	1.446 (3)	C5—H5	0.9300
N1—C7	1.477 (3)	C11—C10	1.446 (4)
C6—C5	1.394 (3)	C11—H11A	0.9700
C6—C7	1.517 (3)	C11—H11B	0.9700
C7—C8	1.516 (4)	C10—H10A	0.9700
C7—H7	0.9800	C10—H10B	0.9700

C9—S1—C10	91.16 (13)	N3—C12—N2	174.7 (3)
C9—N2—C12	118.0 (2)	C3—C2—C1	118.8 (2)
N2—C9—N1	121.8 (2)	C3—C2—H2	120.6
N2—C9—S1	125.49 (18)	C1—C2—H2	120.6
N1—C9—S1	112.73 (17)	C3—C4—C5	118.9 (2)
C2—C1—C6	121.3 (2)	C3—C4—H4	120.6
C2—C1—H1	119.3	C5—C4—H4	120.6
C6—C1—H1	119.3	C4—C3—C2	121.7 (2)
C9—N1—C11	115.4 (2)	C4—C3—Cl1	119.64 (19)
C9—N1—C7	122.06 (19)	C2—C3—Cl1	118.6 (2)
C11—N1—C7	121.9 (2)	C4—C5—C6	121.0 (2)
C1—C6—C5	118.3 (2)	C4—C5—H5	119.5
C1—C6—C7	118.8 (2)	C6—C5—H5	119.5
C5—C6—C7	122.9 (2)	C10—C11—N1	110.1 (2)
N1—C7—C8	110.2 (2)	C10—C11—H11A	109.6
N1—C7—C6	109.10 (19)	N1—C11—H11A	109.6
C8—C7—C6	116.0 (2)	C10—C11—H11B	109.6
N1—C7—H7	107.0	N1—C11—H11B	109.6
C8—C7—H7	107.0	H11A—C11—H11B	108.1
C6—C7—H7	107.0	C11—C10—S1	109.6 (2)
C7—C8—H8A	109.5	C11—C10—H10A	109.7
C7—C8—H8B	109.5	S1—C10—H10A	109.7
H8A—C8—H8B	109.5	C11—C10—H10B	109.7
C7—C8—H8C	109.5	S1—C10—H10B	109.7
H8A—C8—H8C	109.5	H10A—C10—H10B	108.2
H8B—C8—H8C	109.5

C12—N2—C9—N1	−177.6 (2)	C1—C6—C7—C8	152.3 (2)
C12—N2—C9—S1	2.1 (3)	C5—C6—C7—C8	−30.3 (3)
C10—S1—C9—N2	179.1 (3)	C9—N2—C12—N3	177 (100)
C10—S1—C9—N1	−1.1 (2)	C6—C1—C2—C3	1.1 (4)
N2—C9—N1—C11	−173.2 (2)	C5—C4—C3—C2	−0.6 (4)
S1—C9—N1—C11	7.0 (3)	C5—C4—C3—Cl1	179.5 (2)
N2—C9—N1—C7	−2.4 (4)	C1—C2—C3—C4	−0.2 (4)
S1—C9—N1—C7	177.89 (18)	C1—C2—C3—Cl1	179.7 (2)
C2—C1—C6—C5	−1.1 (4)	C3—C4—C5—C6	0.6 (4)
C2—C1—C6—C7	176.5 (2)	C1—C6—C5—C4	0.2 (4)
C9—N1—C7—C8	−98.3 (3)	C7—C6—C5—C4	−177.3 (2)
C11—N1—C7—C8	72.0 (3)	C9—N1—C11—C10	−10.7 (4)
C9—N1—C7—C6	133.2 (2)	C7—N1—C11—C10	178.5 (3)
C11—N1—C7—C6	−56.5 (3)	N1—C11—C10—S1	9.2 (4)
C1—C6—C7—N1	−82.5 (3)	C9—S1—C10—C11	−4.8 (3)
C5—C6—C7—N1	94.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···S1ⁱ	0.97	2.87	3.799 (4)	160

Symmetry code: (i) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClN₃S
M_r	265.76
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	113
a, b, c (Å)	5.8850 (12), 7.5965 (15), 28.273 (6)
V (Å³)	1264.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Saturn
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.940, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	9219, 3019, 2640
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.113, 1.06
No. of reflections	3019
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.34
Absolute structure	Flack (1983), 6200 Friedel pairs

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···S1ⁱ	0.97	2.87	3.799 (4)	159.8

Symmetry code: (i) −x, y−1/2, −z+3/2.

References

Cunico, W., Gomes, C. R. B., Wardell, S. M. S. V., Low, J. N. & Glidewell, C. (2007). Acta Cryst. C63, o411–o414. Web of Science CSD CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hense, A., Fischer, A. & Gesing, E. R. (2002). WO Patent 2002096872. Google Scholar
Jeschke, P., Beck, M. E. & Kraemer, W. (2002). German Patent 10119423. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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