2-{3-[1-(3,4-Dichloro­phen­yl)eth­yl]-1,3-thia­zolidin-2-yl­idene}malononitrile

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

doi:10.1107/S1600536810024049

organic compounds

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Volume 66| Part 7| July 2010| Page o1827

doi:10.1107/S1600536810024049

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2-{3-[1-(3,4-Dichlorophenyl)ethyl]-1,3-thiazolidin-2-ylidene}malononitrile

Xiao-jun Zhang,^a Hong-xin Li ^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: qknhs@yahoo.com.cn

(Received 7 June 2010; accepted 21 June 2010; online 26 June 2010)

In the title compound, C₁₄H₁₁Cl₂N₃S, the thiazole ring is in an envelope conformation with the –CH₂– group bonded to the S atom forming the flap. The crystal structure is stabilized by weak intermolecular C—H⋯Cl and C—H⋯N hydrogen bonds.

Related literature

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

Experimental

Crystal data

C₁₄H₁₁Cl₂N₃S
M_r = 324.22
Monoclinic, P 2₁ /n
a = 7.5900 (15) Å
b = 14.957 (3) Å
c = 12.783 (3) Å
β = 99.03 (3)°
V = 1433.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.59 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 = 0.922, T_max = 0.943
8837 measured reflections
2493 independent reflections
2374 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.102
S = 1.17
2493 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯N3ⁱ	0.99	2.57	3.477 (4)	153
C7—H7A⋯Cl2ⁱⁱ	1.00	2.83	3.623 (3)	137
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z.

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: 10.1107/S1600536810024049/lh5066sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024049/lh5066Isup2.hkl

checkCIF report

Comment top

Recently, compounds containing the 2-(thiazolidin-2-ylidene)malononitrile group have attracted much interest because compounds containing a thiazole ring system are well known as efficient insecticides and pesticides (Hense, et al., 2002). In an attempt to synthesize these types of compounds with higher biological activity the title compound (I) was synthesized and its crystal structure is reported herein.

In (I) (Fig. 1), the bond lengths angles are normal and in a agreement with those common to a previously reported structure (Cunico, et al., 2007). The thiazole ring is in an envelope conformation with the -CH₂- group bonded to the S atom forming the flap. The crystal structure is stabilized by weak intermolecular C—H···Cl and C—H···N hydrogen bonds.

Related literature top

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

Experimental top

Following the procedure of Jeschke, et al. (2002) 2-(thiazolidin-2-ylidene)malononitrile 15.1 g(0.10 mol) and potassium carbonate 16.6 g(0.12 mmol) were dissolved in N,N-dimethylformamide(DMF) (55 ml) and stirred 0.5 h at room temperature. Then 1,2-dichloro-4-(1-chloroethyl)benzene 20.9 g (0.10 mmol) was added, dropwise within 2 h at 318 K. The mixture was then stirred for 8 h at 358 K. After cooling at room temperature, 20 ml of water 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 obtaining the oily product which was rerystallized from methanol to afford the title compound 26.8 g (83% yield). Single crystals suitable for X-ray measurement were obtained by recrystallization of the title compound from a mixture of acetone and methanol at room temperature.

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 50% probability level.

2-{3-[1-(3,4-Dichlorophenyl)ethyl]-1,3-thiazolidin-2-ylidene}malononitrile top

Crystal data top

C₁₄H₁₁Cl₂N₃S	F(000) = 664
M_r = 324.22	D_x = 1.503 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3119 reflections
a = 7.5900 (15) Å	θ = 2.1–27.2°
b = 14.957 (3) Å	µ = 0.59 mm⁻¹
c = 12.783 (3) Å	T = 113 K
β = 99.03 (3)°	Prism, black
V = 1433.2 (5) Å³	0.14 × 0.12 × 0.10 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2493 independent reflections
Radiation source: fine-focus sealed tube	2374 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.7°
ω scans	h = −9→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
T_min = 0.922, T_max = 0.943	l = −15→13
8837 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0287P)² + 2.7247P] where P = (F_o² + 2F_c²)/3
2493 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₁Cl₂N₃S	V = 1433.2 (5) Å³
M_r = 324.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5900 (15) Å	µ = 0.59 mm⁻¹
b = 14.957 (3) Å	T = 113 K
c = 12.783 (3) Å	0.14 × 0.12 × 0.10 mm
β = 99.03 (3)°

Data collection top

Rigaku Saturn diffractometer	2493 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2374 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.943	R_int = 0.032
8837 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.17	Δρ_max = 0.98 e Å⁻³
2493 reflections	Δρ_min = −0.31 e Å⁻³
182 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	0.64889 (9)	0.08386 (5)	−0.14263 (5)	0.01840 (19)
Cl1	0.92712 (10)	0.58799 (5)	0.13883 (6)	0.0241 (2)
Cl2	0.74727 (10)	0.62951 (5)	−0.09604 (6)	0.0243 (2)
N1	0.7016 (3)	0.19511 (15)	0.01236 (18)	0.0156 (5)
N2	0.2888 (3)	0.16439 (17)	0.1598 (2)	0.0228 (6)
N3	0.1985 (3)	0.01685 (18)	−0.1358 (2)	0.0276 (6)
C1	0.5784 (4)	0.13843 (17)	−0.0353 (2)	0.0146 (6)
C2	0.8768 (4)	0.1872 (2)	−0.0228 (2)	0.0194 (6)
H2A	0.9508	0.1414	0.0192	0.023*
H2B	0.9410	0.2450	−0.0150	0.023*
C3	0.8370 (4)	0.1601 (2)	−0.1382 (2)	0.0199 (6)
H3A	0.9408	0.1297	−0.1607	0.024*
H3B	0.8047	0.2127	−0.1843	0.024*
C4	0.4095 (4)	0.11831 (18)	−0.0098 (2)	0.0161 (6)
C5	0.3460 (4)	0.14437 (18)	0.0850 (2)	0.0174 (6)
C6	0.2938 (4)	0.06174 (19)	−0.0798 (2)	0.0184 (6)
C7	0.6790 (4)	0.26246 (19)	0.0927 (2)	0.0177 (6)
H7A	0.5539	0.2575	0.1076	0.021*
C8	0.8041 (4)	0.2423 (2)	0.1955 (2)	0.0242 (7)
H8A	0.7885	0.1800	0.2160	0.036*
H8B	0.7762	0.2821	0.2516	0.036*
H8C	0.9279	0.2518	0.1850	0.036*
C9	0.6999 (4)	0.35513 (18)	0.0458 (2)	0.0158 (6)
C10	0.7943 (4)	0.42212 (19)	0.1048 (2)	0.0178 (6)
H10A	0.8506	0.4103	0.1752	0.021*
C11	0.8072 (4)	0.50688 (18)	0.0613 (2)	0.0173 (6)
C12	0.7274 (4)	0.52438 (19)	−0.0414 (2)	0.0187 (6)
C13	0.6305 (4)	0.45847 (19)	−0.1013 (2)	0.0197 (6)
H13A	0.5743	0.4708	−0.1716	0.024*
C14	0.6165 (4)	0.37428 (19)	−0.0575 (2)	0.0186 (6)
H14A	0.5494	0.3291	−0.0981	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0204 (4)	0.0169 (4)	0.0180 (4)	0.0004 (3)	0.0032 (3)	−0.0022 (3)
Cl1	0.0280 (4)	0.0179 (4)	0.0271 (4)	−0.0050 (3)	0.0062 (3)	−0.0057 (3)
Cl2	0.0257 (4)	0.0176 (4)	0.0315 (4)	0.0026 (3)	0.0111 (3)	0.0080 (3)
N1	0.0142 (12)	0.0136 (12)	0.0192 (12)	−0.0005 (9)	0.0035 (9)	0.0004 (9)
N2	0.0222 (13)	0.0214 (13)	0.0257 (14)	−0.0027 (10)	0.0068 (11)	0.0004 (11)
N3	0.0236 (14)	0.0267 (15)	0.0314 (15)	−0.0036 (11)	0.0010 (12)	−0.0027 (12)
C1	0.0171 (14)	0.0111 (13)	0.0149 (13)	0.0047 (10)	0.0002 (11)	0.0030 (10)
C2	0.0134 (14)	0.0202 (15)	0.0250 (15)	−0.0009 (11)	0.0038 (11)	−0.0006 (12)
C3	0.0170 (14)	0.0221 (15)	0.0217 (15)	−0.0002 (12)	0.0063 (12)	0.0011 (12)
C4	0.0170 (14)	0.0119 (13)	0.0183 (14)	−0.0010 (11)	−0.0005 (11)	0.0021 (11)
C5	0.0141 (14)	0.0124 (14)	0.0248 (16)	0.0001 (10)	0.0001 (12)	0.0037 (12)
C6	0.0177 (14)	0.0183 (15)	0.0198 (15)	0.0008 (12)	0.0047 (12)	0.0037 (12)
C7	0.0170 (14)	0.0177 (15)	0.0193 (15)	−0.0024 (11)	0.0061 (11)	−0.0039 (11)
C8	0.0330 (17)	0.0201 (15)	0.0191 (15)	−0.0044 (13)	0.0032 (13)	0.0022 (12)
C9	0.0137 (13)	0.0135 (14)	0.0213 (15)	−0.0006 (10)	0.0058 (11)	−0.0005 (11)
C10	0.0168 (14)	0.0203 (15)	0.0174 (14)	0.0020 (11)	0.0059 (11)	−0.0023 (11)
C11	0.0151 (14)	0.0128 (14)	0.0255 (15)	−0.0006 (11)	0.0074 (11)	−0.0044 (11)
C12	0.0186 (14)	0.0162 (14)	0.0232 (15)	0.0030 (11)	0.0095 (12)	0.0035 (12)
C13	0.0178 (14)	0.0222 (15)	0.0195 (15)	0.0039 (12)	0.0040 (11)	0.0016 (12)
C14	0.0149 (14)	0.0186 (15)	0.0219 (15)	−0.0018 (11)	0.0019 (11)	−0.0032 (12)

Geometric parameters (Å, º) top

S1—C1	1.751 (3)	C4—C6	1.429 (4)
S1—C3	1.821 (3)	C7—C8	1.526 (4)
Cl1—C11	1.732 (3)	C7—C9	1.528 (4)
Cl2—C12	1.736 (3)	C7—H7A	1.0000
N1—C1	1.336 (3)	C8—H8A	0.9800
N1—C7	1.468 (3)	C8—H8B	0.9800
N1—C2	1.474 (4)	C8—H8C	0.9800
N2—C5	1.150 (4)	C9—C10	1.384 (4)
N3—C6	1.151 (4)	C9—C14	1.402 (4)
C1—C4	1.404 (4)	C10—C11	1.394 (4)
C2—C3	1.514 (4)	C10—H10A	0.9500
C2—H2A	0.9900	C11—C12	1.382 (4)
C2—H2B	0.9900	C12—C13	1.386 (4)
C3—H3A	0.9900	C13—C14	1.389 (4)
C3—H3B	0.9900	C13—H13A	0.9500
C4—C5	1.427 (4)	C14—H14A	0.9500

C1—S1—C3	91.05 (13)	N1—C7—H7A	107.6
C1—N1—C7	127.2 (2)	C8—C7—H7A	107.6
C1—N1—C2	114.2 (2)	C9—C7—H7A	107.6
C7—N1—C2	118.6 (2)	C7—C8—H8A	109.5
N1—C1—C4	129.0 (3)	C7—C8—H8B	109.5
N1—C1—S1	112.0 (2)	H8A—C8—H8B	109.5
C4—C1—S1	119.0 (2)	C7—C8—H8C	109.5
N1—C2—C3	105.5 (2)	H8A—C8—H8C	109.5
N1—C2—H2A	110.6	H8B—C8—H8C	109.5
C3—C2—H2A	110.6	C10—C9—C14	118.9 (3)
N1—C2—H2B	110.6	C10—C9—C7	121.3 (2)
C3—C2—H2B	110.6	C14—C9—C7	119.7 (2)
H2A—C2—H2B	108.8	C9—C10—C11	120.3 (3)
C2—C3—S1	103.50 (19)	C9—C10—H10A	119.9
C2—C3—H3A	111.1	C11—C10—H10A	119.9
S1—C3—H3A	111.1	C12—C11—C10	120.2 (3)
C2—C3—H3B	111.1	C12—C11—Cl1	121.6 (2)
S1—C3—H3B	111.1	C10—C11—Cl1	118.2 (2)
H3A—C3—H3B	109.0	C11—C12—C13	120.3 (3)
C1—C4—C5	125.5 (2)	C11—C12—Cl2	120.0 (2)
C1—C4—C6	118.4 (3)	C13—C12—Cl2	119.6 (2)
C5—C4—C6	115.9 (2)	C12—C13—C14	119.3 (3)
N2—C5—C4	177.5 (3)	C12—C13—H13A	120.3
N3—C6—C4	179.0 (3)	C14—C13—H13A	120.3
N1—C7—C8	110.0 (2)	C13—C14—C9	120.9 (3)
N1—C7—C9	108.5 (2)	C13—C14—H14A	119.6
C8—C7—C9	115.4 (2)	C9—C14—H14A	119.6

C7—N1—C1—C4	−11.5 (4)	C1—N1—C7—C9	−114.5 (3)
C2—N1—C1—C4	169.1 (3)	C2—N1—C7—C9	64.9 (3)
C7—N1—C1—S1	169.1 (2)	N1—C7—C9—C10	−138.4 (3)
C2—N1—C1—S1	−10.3 (3)	C8—C7—C9—C10	−14.5 (4)
C3—S1—C1—N1	−11.7 (2)	N1—C7—C9—C14	44.2 (3)
C3—S1—C1—C4	168.8 (2)	C8—C7—C9—C14	168.0 (3)
C1—N1—C2—C3	32.4 (3)	C14—C9—C10—C11	−0.6 (4)
C7—N1—C2—C3	−147.1 (2)	C7—C9—C10—C11	−178.1 (2)
N1—C2—C3—S1	−37.5 (2)	C9—C10—C11—C12	−0.7 (4)
C1—S1—C3—C2	28.5 (2)	C9—C10—C11—Cl1	−180.0 (2)
N1—C1—C4—C5	−11.2 (5)	C10—C11—C12—C13	1.5 (4)
S1—C1—C4—C5	168.2 (2)	Cl1—C11—C12—C13	−179.3 (2)
N1—C1—C4—C6	173.6 (3)	C10—C11—C12—Cl2	−178.8 (2)
S1—C1—C4—C6	−7.0 (3)	Cl1—C11—C12—Cl2	0.4 (3)
C1—C4—C5—N2	169 (7)	C11—C12—C13—C14	−0.9 (4)
C6—C4—C5—N2	−16 (7)	Cl2—C12—C13—C14	179.4 (2)
C1—C4—C6—N3	−147 (20)	C12—C13—C14—C9	−0.5 (4)
C5—C4—C6—N3	37 (20)	C10—C9—C14—C13	1.2 (4)
C1—N1—C7—C8	118.5 (3)	C7—C9—C14—C13	178.8 (3)
C2—N1—C7—C8	−62.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N3ⁱ	0.99	2.57	3.477 (4)	153
C7—H7A···Cl2ⁱⁱ	1.00	2.83	3.623 (3)	137

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁Cl₂N₃S
M_r	324.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	7.5900 (15), 14.957 (3), 12.783 (3)
β (°)	99.03 (3)
V (Å³)	1433.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.922, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	8837, 2493, 2374
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.102, 1.17
No. of reflections	2493
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.31

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
C3—H3A···N3ⁱ	0.99	2.57	3.477 (4)	153.1
C7—H7A···Cl2ⁱⁱ	1.00	2.83	3.623 (3)	136.9

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z.

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
Hense, A., Fischer, R. & Gesing, E. R. (2002). WO Patent 2002096872. Google Scholar
Jeschke, P., Beck, M. E. & Kraemer, W. (2002). DE 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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2-{3-[1-(3,4-Di­chloro­phen­yl)eth­yl]-1,3-thia­zolidin-2-yl­­idene}malono­nitrile

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

2-{3-[1-(3,4-Dichlorophenyl)ethyl]-1,3-thiazolidin-2-ylidene}malononitrile