{3-[(2-Chloro-1,3-thia­zol-4-yl)meth­yl]-1,3-thia­zolidin-2-yl­idene­amino}­formonitrile

Li, Y.

doi:10.1107/S1600536810035579

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2530

doi:10.1107/S1600536810035579

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{3-[(2-Chloro-1,3-thiazol-4-yl)methyl]-1,3-thiazolidin-2-ylideneamino}formonitrile

Ying-qi Li ^a ^*

^aVocational–Technical Institute, Xiangtan University, Xiangtan 411100, People's Republic of China
^*Correspondence e-mail: liyingqi01@163.com

(Received 26 August 2010; accepted 3 September 2010; online 11 September 2010)

In the title compound, C₈H₇ClN₄S₂, the dihedral angle between the thiazolidine ring (r.m.s. deviation = 0.028 Å) and the thiazole ring (r.m.s. deviation = 0.004 Å) is 74.74 (6)°. The formonitrile group is almost coplanar with the attached ring [C—N—C—N torsion angle = 167 (2)°.

Related literature

For the biological activity of compounds containing a thiazole ring, see: Ehrenfreund et al. (2003 ); Kim et al. (2002 ); Maienfisch & Gsell (1998 ); Shiga et al. (2003 ); Smith & Hunter (2001 ); Tanaka et al. (2005 ). For the bioactivity of 1,3-thiazolidine derivatives, see: Albrecht et al. (2005 ); Liu & Li (2000 ); Ueda et al. (2004 ); Yeh & Chen (2002 ).

Experimental

Crystal data

C₈H₇ClN₄S₂
M_r = 258.75
Monoclinic, P 2₁ /n
a = 6.1731 (9) Å
b = 16.807 (2) Å
c = 10.9057 (14) Å
β = 105.846 (2)°
V = 1088.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 294 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.860, T_max = 0.884
6141 measured reflections
2220 independent reflections
1862 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.103
S = 1.05
2220 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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 global, I. DOI: 10.1107/S1600536810035579/ci5173sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035579/ci5173Isup2.hkl

checkCIF report

Comment top

Recently, compounds containing thiazole ring have been reported to possess various biological activities such as fungicidal, insecticidal, and anticancer activities (Maienfisch & Gsell, 1998; Smith et al., 2001; Kim et al., 2002; Ehrenfreund et al., 2003; Shiga et al., 2003; Tanaka et al., 2005). In addition, 1,3-thiazolidine ring is an important heterocycle scaffold among thiazole compounds. In the past few years lots of 1,3-thiazolidine derivatives have attracted intense attention in medicinal research due to their broad spectrum bioactivities (Liu et al., 2000; Yeh et al., 2002; Ueda et al., 2004;Albrecht et al., 2005). In order to discover more biologically active thiazole compounds, we synthesized thiazole compounds containing 1,3-thiazolidine ring and we report here the crystal structure of the title compound.

The molecule of the title compound (Fig.1) contains two planar rings, the substituted 1,3-thiazolidine ring (S1/C1/C2/N1/C3, r.m.s. deviation 0.028 Å) and the thiazole ring (S2/C8/N4/C6/C7, r.m.s. deviation 0.004 Å). The dihedral angle between the planes of 1,3-thiazolidine ring and thiazole ring is 74.74 (6)°.

Related literature top

For the biological activity of compounds containing a thiazole ring, see: Ehrenfreund et al. (2003); Kim et al. (2002); Maienfisch & Gsell (1998); Shiga et al. (2003); Smith & Hunter (2001); Tanaka et al. (2005). For the bioactivity of 1,3-thiazolidine derivatives, see: Albrecht et al. (2005); Liu & Li (2000); Ueda et al. (2004); Yeh & Chen (2002).

Experimental top

To a stirred solution of 2-cyanoimino-1,3-thiazolidine (1.27 g, 0.01 mol), potassium carbonate (1.66 g,0.012 mol) in 20 ml of acetonitrile was added dropwise a solution of 2-chloro-4-(chloromethyl)thiazole (1.68 g, 0.01 mol) in 15 ml of acetonitrile. The reaction mixture was heated to 333 K for 12 h and then filtered. The solvent was removed to give a solid product, which was recrystallized from ethyl acetate to afford colourless crystals.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

{3-[(2-Chloro-1,3-thiazol-4-yl)methyl]-1,3-thiazolidin-2- ylideneamino}formonitrile top

Crystal data top

C₈H₇ClN₄S₂	F(000) = 528
M_r = 258.75	D_x = 1.579 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3431 reflections
a = 6.1731 (9) Å	θ = 2.4–26.2°
b = 16.807 (2) Å	µ = 0.70 mm⁻¹
c = 10.9057 (14) Å	T = 294 K
β = 105.846 (2)°	Monoclinic, colourless
V = 1088.5 (3) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2220 independent reflections
Radiation source: fine-focus sealed tube	1862 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.860, T_max = 0.884	k = −15→21
6141 measured reflections	l = −11→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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0573P)² + 0.3256P] where P = (F_o² + 2F_c²)/3
2220 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₈H₇ClN₄S₂	V = 1088.5 (3) Å³
M_r = 258.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.1731 (9) Å	µ = 0.70 mm⁻¹
b = 16.807 (2) Å	T = 294 K
c = 10.9057 (14) Å	0.22 × 0.20 × 0.18 mm
β = 105.846 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2220 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1862 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.884	R_int = 0.021
6141 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.05	Δρ_max = 0.30 e Å⁻³
2220 reflections	Δρ_min = −0.34 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
Cl1	−0.27073 (11)	0.02267 (4)	0.65605 (6)	0.0705 (2)
S1	0.70384 (10)	0.09234 (4)	1.21031 (5)	0.0588 (2)
S2	0.07788 (10)	0.10824 (3)	0.56567 (5)	0.05097 (18)
N1	0.4957 (3)	0.15672 (9)	0.99768 (14)	0.0389 (4)
N2	0.3327 (3)	0.18765 (11)	1.15862 (15)	0.0466 (4)
N3	0.3408 (4)	0.18457 (14)	1.38596 (19)	0.0669 (6)
N4	0.0452 (3)	0.11665 (10)	0.79535 (15)	0.0410 (4)
C1	0.8149 (4)	0.07222 (18)	1.0769 (2)	0.0660 (7)
H1A	0.9724	0.0873	1.0975	0.079*
H1B	0.8034	0.0159	1.0571	0.079*
C2	0.6843 (4)	0.11841 (17)	0.9667 (2)	0.0631 (7)
H2A	0.7801	0.1583	0.9440	0.076*
H2B	0.6296	0.0834	0.8942	0.076*
C3	0.4872 (3)	0.15132 (11)	1.11773 (17)	0.0370 (4)
C4	0.3448 (4)	0.18300 (13)	1.2819 (2)	0.0478 (5)
C5	0.3492 (3)	0.20877 (12)	0.90364 (17)	0.0426 (4)
H5A	0.4394	0.2499	0.8790	0.051*
H5B	0.2428	0.2346	0.9417	0.051*
C6	0.2233 (3)	0.16430 (11)	0.78796 (17)	0.0378 (4)
C7	0.2661 (4)	0.16624 (12)	0.67255 (17)	0.0451 (5)
H7	0.3818	0.1951	0.6541	0.054*
C8	−0.0433 (3)	0.08538 (11)	0.68491 (19)	0.0428 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0659 (4)	0.0730 (4)	0.0743 (4)	−0.0187 (3)	0.0221 (3)	−0.0253 (3)
S1	0.0642 (4)	0.0707 (4)	0.0407 (3)	0.0175 (3)	0.0133 (3)	0.0086 (3)
S2	0.0674 (4)	0.0577 (3)	0.0290 (3)	0.0066 (3)	0.0152 (2)	−0.0030 (2)
N1	0.0391 (8)	0.0492 (9)	0.0307 (8)	0.0022 (7)	0.0131 (6)	−0.0022 (7)
N2	0.0483 (9)	0.0586 (10)	0.0382 (9)	0.0007 (8)	0.0208 (7)	−0.0049 (7)
N3	0.0869 (15)	0.0758 (14)	0.0499 (11)	−0.0106 (11)	0.0390 (11)	−0.0082 (10)
N4	0.0470 (9)	0.0462 (9)	0.0335 (8)	0.0025 (7)	0.0174 (7)	−0.0024 (7)
C1	0.0546 (13)	0.0878 (18)	0.0591 (14)	0.0197 (13)	0.0218 (11)	0.0030 (13)
C2	0.0664 (15)	0.0811 (17)	0.0517 (13)	0.0266 (13)	0.0328 (12)	0.0063 (12)
C3	0.0369 (9)	0.0420 (10)	0.0328 (9)	−0.0068 (8)	0.0108 (7)	−0.0030 (7)
C4	0.0526 (12)	0.0519 (12)	0.0465 (12)	−0.0061 (9)	0.0264 (9)	−0.0056 (9)
C5	0.0517 (11)	0.0417 (10)	0.0356 (9)	0.0012 (8)	0.0140 (8)	−0.0005 (8)
C6	0.0448 (10)	0.0398 (10)	0.0310 (9)	0.0074 (8)	0.0141 (7)	0.0027 (7)
C7	0.0549 (12)	0.0498 (11)	0.0345 (10)	0.0026 (9)	0.0191 (9)	0.0019 (8)
C8	0.0470 (10)	0.0435 (10)	0.0397 (10)	0.0051 (8)	0.0149 (8)	−0.0041 (8)

Geometric parameters (Å, º) top

Cl1—C8	1.715 (2)	N4—C6	1.380 (2)
S1—C3	1.7471 (19)	C1—C2	1.472 (3)
S1—C1	1.801 (2)	C1—H1A	0.97
S2—C7	1.709 (2)	C1—H1B	0.97
S2—C8	1.711 (2)	C2—H2A	0.97
N1—C3	1.328 (2)	C2—H2B	0.97
N1—C2	1.448 (3)	C5—C6	1.490 (3)
N1—C5	1.459 (2)	C5—H5A	0.97
N2—C3	1.309 (2)	C5—H5B	0.97
N2—C4	1.328 (3)	C6—C7	1.355 (3)
N3—C4	1.142 (3)	C7—H7	0.93
N4—C8	1.291 (2)

C3—S1—C1	92.29 (10)	N2—C3—N1	122.18 (17)
C7—S2—C8	88.08 (10)	N2—C3—S1	125.57 (14)
C3—N1—C2	116.74 (17)	N1—C3—S1	112.25 (14)
C3—N1—C5	123.40 (16)	N3—C4—N2	173.6 (3)
C2—N1—C5	119.09 (15)	N1—C5—C6	111.98 (15)
C3—N2—C4	118.19 (18)	N1—C5—H5A	109.2
C8—N4—C6	108.81 (16)	C6—C5—H5A	109.2
C2—C1—S1	108.40 (16)	N1—C5—H5B	109.2
C2—C1—H1A	110.0	C6—C5—H5B	109.2
S1—C1—H1A	110.0	H5A—C5—H5B	107.9
C2—C1—H1B	110.0	C7—C6—N4	115.37 (17)
S1—C1—H1B	110.0	C7—C6—C5	125.85 (19)
H1A—C1—H1B	108.4	N4—C6—C5	118.78 (16)
N1—C2—C1	109.89 (18)	C6—C7—S2	110.57 (16)
N1—C2—H2A	109.7	C6—C7—H7	124.7
C1—C2—H2A	109.7	S2—C7—H7	124.7
N1—C2—H2B	109.7	N4—C8—S2	117.15 (16)
C1—C2—H2B	109.7	N4—C8—Cl1	122.55 (16)
H2A—C2—H2B	108.2	S2—C8—Cl1	120.29 (12)

C3—S1—C1—C2	4.2 (2)	C3—N1—C5—C6	−124.90 (19)
C3—N1—C2—C1	6.9 (3)	C2—N1—C5—C6	65.5 (2)
C5—N1—C2—C1	177.2 (2)	C8—N4—C6—C7	−1.2 (2)
S1—C1—C2—N1	−6.7 (3)	C8—N4—C6—C5	178.42 (17)
C4—N2—C3—N1	−175.95 (18)	N1—C5—C6—C7	−106.0 (2)
C4—N2—C3—S1	3.3 (3)	N1—C5—C6—N4	74.4 (2)
C2—N1—C3—N2	175.7 (2)	N4—C6—C7—S2	0.9 (2)
C5—N1—C3—N2	5.9 (3)	C5—C6—C7—S2	−178.68 (15)
C2—N1—C3—S1	−3.7 (2)	C8—S2—C7—C6	−0.28 (16)
C5—N1—C3—S1	−173.46 (14)	C6—N4—C8—S2	1.0 (2)
C1—S1—C3—N2	−179.83 (19)	C6—N4—C8—Cl1	−179.65 (14)
C1—S1—C3—N1	−0.49 (17)	C7—S2—C8—N4	−0.42 (17)
C3—N2—C4—N3	167 (2)	C7—S2—C8—Cl1	−179.83 (14)

Experimental details

Crystal data
Chemical formula	C₈H₇ClN₄S₂
M_r	258.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	6.1731 (9), 16.807 (2), 10.9057 (14)
β (°)	105.846 (2)
V (Å³)	1088.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.860, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	6141, 2220, 1862
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.103, 1.05
No. of reflections	2220
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.34

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

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