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

Liu, L.; Song, T.; Xu, L.

doi:10.1107/S1600536811023737

organic compounds

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doi:10.1107/S1600536811023737

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

Lei Liu,^a Tao Song ^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: blessliulei@126.com

(Received 12 June 2011; accepted 17 June 2011; online 22 June 2011)

In the title compound, C₁₄H₁₁F₂N₃S, the heterocyclic five-membered ring has an envelope conformation. Although the molecule is chiral, the compound is a racemate (R/S). There is a weak intermolecular C—H⋯π interaction but no classical hydrogen bonds are observed in the crystal structure.

Related literature

For the biological activity of thiazoles and thiazolidines, see: Melnikov et al. (1979 ); Kratt et al. (1986 ). For the synthesis, see: Hense et al. (2002 ). For a related structure, see: Xu et al. (2005 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₄H₁₁F₂N₃S
M_r = 291.32
Triclinic, $[P \overline 1]$
a = 7.6886 (14) Å
b = 8.9854 (16) Å
c = 10.8188 (19) Å
α = 102.508 (2)°
β = 90.940 (2)°
γ = 112.861 (2)°
V = 668.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.32 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.922, T_max = 0.931
4810 measured reflections
2332 independent reflections
2049 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.116
S = 1.08
2338 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯Cg1ⁱ	0.96	2.94	3.848 (3)	158
Symmetry code: (i) -x, -y+2, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023737/dn2699sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023737/dn2699Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811023737/dn2699Isup3.cml

checkCIF report

Comment top

It has been reported that both thiazoles and thiazolidines have good and wide insecticidal, fungicidal, herbicidal and acaricidal activities (Melnikov, et al., 1979; Kratt et al., 1986). As part of our search for compounds with good herbicidal and fungicidal activity, the title compound, (I), was synthesized.

In (I) The heterocyclic five-membered ring (C1/C13/N1/C14/S1) has an envelope conformation on C13 with puckering parameters, Q(2)= 0.155 (3)Å and ϕ(2) = 108.1 (9)° (Cremer & Pople, 1975) (Fig. 1). The bond lengths and angles are within expected values for the thiazolidin ring (Xu, et al., 2005). The phenyl ring is twisted with respect to the thiazolidin ring with a torsion angle of 138.0 (2)°. No classical hydrogen bonds were found in the crystal, only van der Waals forces and a weak C-H···π interaction involving the Cg1 centroid of a symetry related phenyl ring (Table 1) stabilize the crystal structure.

Related literature top

For the biological activity of thiazoles and thiazolidines, see: Melnikov et al. (1979); Kratt et al. (1986). For the synthetis, see: Hense et al. (2002). For a related structure, see: Xu et al. (2005). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

2-(thiazolidin-2-ylidene)malononitrile 15.5 g (0.1 mol), potassium carbonate 13.8 g (0.1 mol) and acetonitrile 50 g are charged in a flask equipped with stirrer and reflux condenser. The mixture is heated to reflux, then 1-(1-chloroethyl)-2,4-difluorobenzene 17.7 g (0.1 mol) is droped in over 30 minutes. Keep refluxing for 12 h. Upon cooling at room temperature. The reaction mixture is filtered, and the solution is concentrated under reduced pressure to give the title compound (I) 27.2 g (92% yield). (Hense, et al., 2002). Single crystals suitable for X-ray measurement were obtained by recrystallization from the tetrahydrofuran solution of (I) at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound (I), with the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.

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

Crystal data top

C₁₄H₁₁F₂N₃S	Z = 2
M_r = 291.32	F(000) = 300
Triclinic, P1	D_x = 1.448 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6886 (14) Å	Cell parameters from 2422 reflections
b = 8.9854 (16) Å	θ = 2.3–25.1°
c = 10.8188 (19) Å	µ = 0.26 mm⁻¹
α = 102.508 (2)°	T = 296 K
β = 90.940 (2)°	Block, colorless
γ = 112.861 (2)°	0.32 × 0.30 × 0.28 mm
V = 668.1 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2332 independent reflections
Radiation source: fine-focus sealed tube	2049 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.922, T_max = 0.931	k = −10→10
4810 measured reflections	l = −12→12

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0521P)² + 0.2818P] where P = (F_o² + 2F_c²)/3
2338 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₁F₂N₃S	γ = 112.861 (2)°
M_r = 291.32	V = 668.1 (2) Å³
Triclinic, P1	Z = 2
a = 7.6886 (14) Å	Mo Kα radiation
b = 8.9854 (16) Å	µ = 0.26 mm⁻¹
c = 10.8188 (19) Å	T = 296 K
α = 102.508 (2)°	0.32 × 0.30 × 0.28 mm
β = 90.940 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2332 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2049 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.931	R_int = 0.031
4810 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.08	Δρ_max = 0.27 e Å⁻³
2338 reflections	Δρ_min = −0.31 e Å⁻³
182 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.28619 (9)	0.70036 (7)	−0.03503 (5)	0.0493 (2)
F1	−0.19221 (18)	0.68270 (16)	0.17886 (11)	0.0523 (3)
F2	−0.3465 (2)	0.44311 (19)	0.52735 (15)	0.0678 (4)
C1	0.2408 (3)	0.8531 (2)	0.07280 (18)	0.0345 (4)
C2	0.0263 (3)	0.7988 (2)	0.36404 (17)	0.0357 (4)
N1	0.2234 (2)	0.8236 (2)	0.18869 (15)	0.0364 (4)
C3	0.1633 (3)	0.9200 (2)	0.29655 (18)	0.0361 (4)
H3	0.0944	0.9755	0.2609	0.043*
C4	−0.1470 (3)	0.6816 (2)	0.30078 (18)	0.0380 (4)
C5	0.2315 (3)	0.9856 (2)	0.03016 (18)	0.0366 (4)
C6	−0.2757 (3)	0.5620 (3)	0.3520 (2)	0.0463 (5)
H6	−0.3904	0.4852	0.3063	0.056*
C7	0.0653 (3)	0.7939 (3)	0.48932 (19)	0.0419 (5)
H7	0.1785	0.8718	0.5365	0.050*
C8	0.2460 (3)	0.9825 (3)	−0.1015 (2)	0.0439 (5)
C9	0.2356 (3)	1.1362 (3)	0.10832 (19)	0.0409 (5)
N2	0.2449 (3)	1.2619 (2)	0.1680 (2)	0.0598 (6)
C10	−0.2252 (3)	0.5624 (3)	0.4748 (2)	0.0465 (5)
C11	−0.0604 (3)	0.6760 (3)	0.5452 (2)	0.0476 (5)
H11	−0.0328	0.6746	0.6288	0.057*
C12	0.3374 (3)	1.0542 (3)	0.3821 (2)	0.0504 (5)
H12A	0.4102	1.0031	0.4156	0.076*
H12B	0.2974	1.1161	0.4512	0.076*
H12C	0.4140	1.1281	0.3335	0.076*
N3	0.2605 (3)	0.9831 (3)	−0.20641 (19)	0.0652 (6)
C13	0.2830 (4)	0.6928 (3)	0.2078 (2)	0.0634 (7)
H13A	0.4078	0.7428	0.2559	0.076*
H13B	0.1944	0.6238	0.2558	0.076*
C14	0.2883 (5)	0.5919 (4)	0.0852 (3)	0.0751 (8)
H14A	0.1790	0.4861	0.0671	0.090*
H14B	0.4023	0.5701	0.0861	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0637 (4)	0.0392 (3)	0.0472 (3)	0.0227 (3)	0.0196 (3)	0.0102 (2)
F1	0.0570 (8)	0.0552 (8)	0.0364 (6)	0.0142 (6)	−0.0043 (5)	0.0111 (6)
F2	0.0685 (9)	0.0637 (9)	0.0746 (10)	0.0176 (7)	0.0297 (7)	0.0388 (8)
C1	0.0313 (9)	0.0328 (10)	0.0370 (10)	0.0098 (8)	0.0066 (8)	0.0092 (8)
C2	0.0404 (10)	0.0367 (10)	0.0332 (10)	0.0181 (9)	0.0077 (8)	0.0097 (8)
N1	0.0428 (9)	0.0359 (9)	0.0375 (9)	0.0193 (7)	0.0116 (7)	0.0158 (7)
C3	0.0417 (11)	0.0346 (10)	0.0340 (10)	0.0163 (8)	0.0056 (8)	0.0101 (8)
C4	0.0446 (11)	0.0404 (11)	0.0309 (9)	0.0195 (9)	0.0052 (8)	0.0075 (8)
C5	0.0398 (10)	0.0346 (10)	0.0347 (10)	0.0121 (8)	0.0055 (8)	0.0124 (8)
C6	0.0435 (11)	0.0400 (11)	0.0509 (12)	0.0129 (9)	0.0093 (9)	0.0089 (9)
C7	0.0447 (11)	0.0467 (12)	0.0337 (10)	0.0174 (9)	0.0045 (8)	0.0104 (9)
C8	0.0458 (12)	0.0423 (11)	0.0413 (12)	0.0132 (9)	0.0045 (9)	0.0142 (9)
C9	0.0464 (11)	0.0390 (11)	0.0422 (11)	0.0167 (9)	0.0106 (9)	0.0205 (9)
N2	0.0860 (15)	0.0423 (11)	0.0621 (13)	0.0318 (11)	0.0249 (11)	0.0224 (10)
C10	0.0529 (13)	0.0453 (12)	0.0490 (12)	0.0220 (10)	0.0229 (10)	0.0212 (10)
C11	0.0592 (14)	0.0574 (13)	0.0353 (10)	0.0283 (11)	0.0140 (10)	0.0192 (10)
C12	0.0515 (13)	0.0445 (12)	0.0461 (12)	0.0094 (10)	−0.0007 (10)	0.0120 (10)
N3	0.0812 (15)	0.0721 (15)	0.0408 (11)	0.0256 (12)	0.0064 (10)	0.0205 (10)
C13	0.096 (2)	0.0681 (16)	0.0625 (15)	0.0598 (16)	0.0324 (14)	0.0371 (13)
C14	0.124 (3)	0.0629 (16)	0.0657 (17)	0.0628 (18)	0.0195 (16)	0.0223 (13)

Geometric parameters (Å, º) top

S1—C1	1.7490 (19)	C6—C10	1.376 (3)
S1—C14	1.789 (3)	C6—H6	0.9300
F1—C4	1.362 (2)	C7—C11	1.387 (3)
F2—C10	1.359 (2)	C7—H7	0.9300
C1—N1	1.335 (2)	C8—N3	1.144 (3)
C1—C5	1.392 (3)	C9—N2	1.148 (3)
C2—C4	1.386 (3)	C10—C11	1.362 (3)
C2—C7	1.397 (3)	C11—H11	0.9300
C2—C3	1.519 (3)	C12—H12A	0.9600
N1—C13	1.468 (3)	C12—H12B	0.9600
N1—C3	1.488 (2)	C12—H12C	0.9600
C3—C12	1.524 (3)	C13—C14	1.447 (4)
C3—H3	0.9800	C13—H13A	0.9700
C4—C6	1.375 (3)	C13—H13B	0.9700
C5—C9	1.421 (3)	C14—H14A	0.9700
C5—C8	1.425 (3)	C14—H14B	0.9700

C1—S1—C14	91.83 (11)	C2—C7—H7	119.1
N1—C1—C5	129.40 (18)	N3—C8—C5	178.6 (2)
N1—C1—S1	112.28 (14)	N2—C9—C5	176.8 (2)
C5—C1—S1	118.31 (14)	F2—C10—C11	118.9 (2)
C4—C2—C7	115.89 (18)	F2—C10—C6	118.0 (2)
C4—C2—C3	120.40 (17)	C11—C10—C6	123.1 (2)
C7—C2—C3	123.69 (18)	C10—C11—C7	118.5 (2)
C1—N1—C13	114.67 (16)	C10—C11—H11	120.8
C1—N1—C3	124.89 (15)	C7—C11—H11	120.8
C13—N1—C3	120.28 (16)	C3—C12—H12A	109.5
N1—C3—C2	108.53 (15)	C3—C12—H12B	109.5
N1—C3—C12	110.00 (17)	H12A—C12—H12B	109.5
C2—C3—C12	114.49 (16)	C3—C12—H12C	109.5
N1—C3—H3	107.9	H12A—C12—H12C	109.5
C2—C3—H3	107.9	H12B—C12—H12C	109.5
C12—C3—H3	107.9	C14—C13—N1	109.3 (2)
F1—C4—C6	117.54 (18)	C14—C13—H13A	109.8
F1—C4—C2	118.02 (17)	N1—C13—H13A	109.8
C6—C4—C2	124.43 (19)	C14—C13—H13B	109.8
C1—C5—C9	125.92 (17)	N1—C13—H13B	109.8
C1—C5—C8	117.88 (18)	H13A—C13—H13B	108.3
C9—C5—C8	115.58 (17)	C13—C14—S1	109.04 (17)
C4—C6—C10	116.3 (2)	C13—C14—H14A	109.9
C4—C6—H6	121.8	S1—C14—H14A	109.9
C10—C6—H6	121.8	C13—C14—H14B	109.9
C11—C7—C2	121.7 (2)	S1—C14—H14B	109.9
C11—C7—H7	119.1	H14A—C14—H14B	108.3

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···Cg1ⁱ	0.96	2.94	3.848 (3)	158

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁F₂N₃S
M_r	291.32
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.6886 (14), 8.9854 (16), 10.8188 (19)
α, β, γ (°)	102.508 (2), 90.940 (2), 112.861 (2)
V (Å³)	668.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.32 × 0.30 × 0.28

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.922, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	4810, 2332, 2049
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.116, 1.08
No. of reflections	2338
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.31

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···Cg1ⁱ	0.96	2.94	3.848 (3)	158

Symmetry code: (i) −x, −y+2, −z+1.

References

Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358 CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hense, A., Fischer, R., Gesing, E.-R., Herrmann, S., Kather, K., Lehr, S., Voigt, K., Riebel, H.-J., Jeschke, P. & Erdelen, C. (2002). Patent WO 2002096872. Google Scholar
Kratt, G., Salbeck, G., Bonin, W., Bauer, K., Bieringer, H. & Sachse, B. (1986). Patent DE 3505432. Google Scholar
Melnikov, N. N., Grapov, A. F., Razvodovskaya, G. K., Abelentseva, G. M., Sedykh, A. S., Shapovalova, G. K. & Siforova, T. A. (1979). Jpn Patent JP 78103471. 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
Xu, L.-Z., Yu, G.-P., Zhang, P.-Y. & Li, C.-L. (2005). Acta Cryst. E61, o2104–o2105. Web of Science CSD CrossRef IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

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