(Z)-3-Allyl-5-(4-fluoro­benzyl­idene)-2-sulfanyl­idene­thia­zolidin-4-one

El Ajlaoui, R.; Belkhouya, N.; Rakib, E.M.; Mojahidi, S.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314616012360

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161236

doi:10.1107/S2414314616012360

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(Z)-3-Allyl-5-(4-fluorobenzylidene)-2-sulfanylidenethiazolidin-4-one

Rahhal El Ajlaoui,^a ^* Najat Belkhouya,^a El Mostapha Rakib,^a Souad Mojahidi,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Organique et Analytique, Université Sultan Moulay Slimane, Faculté des Sciences et Techniques, Béni-Mellal, BP 523, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: r_elajlaoui@yahoo.fr

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 29 July 2016; accepted 30 July 2016; online 12 August 2016)

In the title compound, C₁₃H₁₀FNOS₂, the sulfanylidenethiazolidine ring and the benzylidene ring are almost coplanar [dihedral angle between the two planes = 0.1 (2)°]. The mean plane through the allyl group is nearly perpendicular to the sulfanylidenethiazolidine ring, as indicated by the dihedral angle of 69.5 (5)° between them. In the crystal, molecules are linked together by weak C—H⋯O hydrogen bonds involving the same acceptor atom, forming dimers parallel to (1-22).

Keywords: crystal structure; fluorobenzylidene; sulfanylidenethiazolidin-4-one; hydrogen bonds.

CCDC reference: 1496946

Structure description

5-Arylidene-2-sulfanylidene-1,3-thiazolidinine-4-ones or 5-arylidene rhodanines are considered to be `privileged scaffolds' in the medicinal chemistry community because they present bioactivity in a large range of derivatives (Mendgen et al., 2012 ; Khazaei et al., 2014 ; Coulibaly et al., 2015 ; Tomasić & Masic et al., 2009 ). For example, these small molecules have been known to possess a wide range of biological properties such as potent and selective inhibitors of the `atypical' dual-specificity phosphatase (DSP) family member-JNK-stimulating phosphatase-1 (JSP-1) (Cutshall et al., 2005 ), as aldose reductase inhibitors in diabetic peripheral neuropathy (Hotta et al., 2006 ), and as DDX3 inhibitors for HIV replication (Maga et al., 2008 ). The unusual biological activities displayed by many rhodanine-based molecules have made them attractive synthetic targets.

The molecule of the title compound is build up from a 4-fluorobenzylidene ring linked to a sulfanylidenethiazolidine ring which is attached to an allyl group as shown in Fig. 1. The 4-fluorobenzylidene and the sulfanylidenethiazolidine rings are virtually coplanar with a maximum deviation from the mean plane of 0.067 (3) Å for the C4 atom. The sulfanylidenethiazolidine ring makes a dihedral angle of 69.5 (5)° with the plan through the allyl group.

Figure 1
Plot of the molecule of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

Structure cohesion is ensured by weak C3—H3⋯O1 and C7—H7⋯O1 hydrogen bonds, forming dimers parallel to (1 $[\overline{2}]$ 2) (see Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.57	3.442 (3)	157
C3—H3⋯O1ⁱ	0.93	2.55	3.407 (4)	154
Symmetry code: (i) -x, -y, -z+1.

Figure 2
Crystal packing for the title compound showing hydrogen bonds as dashed lines.

Synthesis and crystallization

To a solution of 3-allylrhodanine (1.15 mmol, 0.2 g) in 10 ml of THF, (4-fluorobenzylidene)-4-methyl-5-oxopyrazolidin-2-ium-1-ide (1.38 mmol) was added. The mixture was refluxed for 8 h, monitored by TLC, the reaction completed and a yellow spot (TLC R_f = 0.3, using hexane/ethyl acetate 1:9) was generated cleanly. The solvent was evaporated in vacuo. The crude product was purified on silica gel using hexane:ethyl acetate (1:9) as eluent. The title compound was recrystallized from ethanol solution (yield 82%, m.p. 382 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₀FNOS₂
M_r	279.34
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	4.7764 (10), 11.750 (3), 13.067 (3)
α, β, γ (°)	109.917 (10), 99.766 (11), 101.71 (1)
V (Å³)	652.0 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.41
Crystal size (mm)	0.35 × 0.31 × 0.22

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.682, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	17965, 2861, 2035
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.148, 1.07
No. of reflections	2861
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1496946

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616012360/bt4020sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012360/bt4020Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616012360/bt4020Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(Z)-3-Allyl-5-(4-fluorobenzylidene)-2-sulfanylidenethiazolidin-4-one top

Crystal data top

C₁₃H₁₀FNOS₂	F(000) = 288
M_r = 279.34	D_x = 1.423 Mg m⁻³
Triclinic, P1	Melting point: 382 K
a = 4.7764 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.750 (3) Å	Cell parameters from 2861 reflections
c = 13.067 (3) Å	θ = 2.0–27.1°
α = 109.917 (10)°	µ = 0.41 mm⁻¹
β = 99.766 (11)°	T = 296 K
γ = 101.71 (1)°	Block, colourless
V = 652.0 (3) Å³	0.35 × 0.31 × 0.22 mm
Z = 2

Data collection top

Bruker X8 APEX diffractometer	2861 independent reflections
Radiation source: fine-focus sealed tube	2035 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
φ and ω scans	θ_max = 27.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −6→6
T_min = 0.682, T_max = 0.745	k = −15→15
17965 measured reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.148	w = 1/[σ²(F_o²) + (0.0706P)² + 0.2274P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2861 reflections	Δρ_max = 0.54 e Å⁻³
163 parameters	Δρ_min = −0.23 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3197 (8)	0.5284 (3)	0.8728 (3)	0.0779 (9)
C2	0.1461 (9)	0.4097 (3)	0.8479 (3)	0.0892 (10)
H2	0.0260	0.3950	0.8937	0.107*
C3	0.1524 (7)	0.3124 (3)	0.7538 (3)	0.0712 (8)
H3	0.0352	0.2313	0.7363	0.085*
C4	0.3302 (6)	0.3326 (2)	0.6844 (2)	0.0551 (6)
C5	0.4984 (7)	0.4560 (3)	0.7132 (3)	0.0751 (8)
H5	0.6170	0.4729	0.6676	0.090*
C6	0.4931 (8)	0.5531 (3)	0.8072 (3)	0.0825 (9)
H6	0.6075	0.6349	0.8255	0.099*
C7	0.3191 (6)	0.2259 (2)	0.5854 (2)	0.0555 (6)
H7	0.1924	0.1501	0.5771	0.067*
C8	0.4594 (5)	0.2170 (2)	0.5034 (2)	0.0541 (6)
C9	0.4088 (6)	0.0954 (2)	0.4106 (2)	0.0552 (6)
C10	0.7549 (5)	0.2276 (3)	0.3625 (2)	0.0572 (6)
C11	0.5746 (7)	−0.0010 (3)	0.2381 (3)	0.0695 (8)
H11A	0.5181	−0.0773	0.2521	0.083*
H11B	0.7706	0.0073	0.2253	0.083*
C12	0.3616 (9)	−0.0127 (3)	0.1352 (3)	0.0865 (10)
H12	0.3827	0.0586	0.1179	0.104*
C13	0.1561 (11)	−0.1087 (4)	0.0692 (4)	0.1183 (15)
H13A	0.1254	−0.1825	0.0826	0.142*
H13B	0.0348	−0.1060	0.0069	0.142*
N1	0.5847 (4)	0.1081 (2)	0.33787 (18)	0.0548 (5)
O1	0.2415 (5)	−0.00459 (18)	0.39528 (17)	0.0744 (6)
F1	0.3139 (6)	0.6243 (2)	0.9653 (2)	0.1186 (8)
S1	0.71039 (14)	0.33471 (6)	0.48434 (6)	0.0600 (2)
S2	0.97365 (17)	0.26959 (8)	0.29023 (8)	0.0789 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.098 (2)	0.0623 (18)	0.078 (2)	0.0303 (17)	0.0374 (18)	0.0207 (16)
C2	0.113 (3)	0.075 (2)	0.088 (2)	0.0225 (19)	0.058 (2)	0.0293 (18)
C3	0.0802 (19)	0.0576 (16)	0.0754 (19)	0.0085 (14)	0.0317 (16)	0.0262 (14)
C4	0.0559 (14)	0.0505 (13)	0.0600 (15)	0.0112 (11)	0.0151 (11)	0.0248 (12)
C5	0.085 (2)	0.0580 (17)	0.082 (2)	0.0083 (14)	0.0378 (17)	0.0262 (15)
C6	0.100 (2)	0.0478 (16)	0.093 (2)	0.0098 (15)	0.038 (2)	0.0194 (15)
C7	0.0557 (14)	0.0472 (13)	0.0619 (15)	0.0057 (11)	0.0148 (12)	0.0245 (12)
C8	0.0519 (13)	0.0492 (13)	0.0603 (15)	0.0050 (10)	0.0120 (11)	0.0265 (12)
C9	0.0553 (14)	0.0487 (13)	0.0597 (15)	0.0081 (11)	0.0154 (12)	0.0221 (12)
C10	0.0454 (13)	0.0613 (15)	0.0719 (17)	0.0140 (11)	0.0146 (11)	0.0351 (13)
C11	0.0727 (18)	0.0614 (17)	0.080 (2)	0.0218 (14)	0.0346 (16)	0.0255 (15)
C12	0.115 (3)	0.067 (2)	0.068 (2)	0.0179 (19)	0.0249 (19)	0.0192 (16)
C13	0.154 (4)	0.088 (3)	0.092 (3)	0.031 (3)	0.015 (3)	0.020 (2)
N1	0.0520 (11)	0.0556 (12)	0.0603 (13)	0.0130 (9)	0.0187 (10)	0.0261 (10)
O1	0.0830 (13)	0.0523 (11)	0.0776 (13)	−0.0033 (9)	0.0305 (11)	0.0210 (9)
F1	0.168 (2)	0.0730 (13)	0.1117 (17)	0.0337 (13)	0.0750 (16)	0.0134 (11)
S1	0.0534 (4)	0.0515 (4)	0.0731 (5)	0.0033 (3)	0.0190 (3)	0.0271 (3)
S2	0.0669 (5)	0.0865 (6)	0.0954 (6)	0.0129 (4)	0.0382 (4)	0.0469 (5)

Geometric parameters (Å, º) top

C1—C6	1.348 (5)	C8—S1	1.754 (2)
C1—F1	1.351 (3)	C9—O1	1.210 (3)
C1—C2	1.367 (5)	C9—N1	1.395 (3)
C2—C3	1.374 (4)	C10—N1	1.370 (3)
C2—H2	0.9300	C10—S2	1.634 (3)
C3—C4	1.388 (4)	C10—S1	1.738 (3)
C3—H3	0.9300	C11—N1	1.470 (3)
C4—C5	1.394 (4)	C11—C12	1.488 (5)
C4—C7	1.446 (4)	C11—H11A	0.9700
C5—C6	1.371 (4)	C11—H11B	0.9700
C5—H5	0.9300	C12—C13	1.257 (5)
C6—H6	0.9300	C12—H12	0.9300
C7—C8	1.343 (4)	C13—H13A	0.9300
C7—H7	0.9300	C13—H13B	0.9300
C8—C9	1.466 (4)

C6—C1—F1	119.0 (3)	C9—C8—S1	109.58 (18)
C6—C1—C2	122.1 (3)	O1—C9—N1	122.3 (2)
F1—C1—C2	118.9 (3)	O1—C9—C8	127.1 (2)
C1—C2—C3	118.8 (3)	N1—C9—C8	110.6 (2)
C1—C2—H2	120.6	N1—C10—S2	126.4 (2)
C3—C2—H2	120.6	N1—C10—S1	110.99 (19)
C2—C3—C4	121.4 (3)	S2—C10—S1	122.59 (16)
C2—C3—H3	119.3	N1—C11—C12	112.2 (2)
C4—C3—H3	119.3	N1—C11—H11A	109.2
C3—C4—C5	117.1 (3)	C12—C11—H11A	109.2
C3—C4—C7	118.1 (2)	N1—C11—H11B	109.2
C5—C4—C7	124.7 (2)	C12—C11—H11B	109.2
C6—C5—C4	121.5 (3)	H11A—C11—H11B	107.9
C6—C5—H5	119.2	C13—C12—C11	126.9 (4)
C4—C5—H5	119.2	C13—C12—H12	116.6
C1—C6—C5	119.1 (3)	C11—C12—H12	116.6
C1—C6—H6	120.5	C12—C13—H13A	120.0
C5—C6—H6	120.5	C12—C13—H13B	120.0
C8—C7—C4	131.4 (2)	H13A—C13—H13B	120.0
C8—C7—H7	114.3	C10—N1—C9	116.2 (2)
C4—C7—H7	114.3	C10—N1—C11	122.7 (2)
C7—C8—C9	120.7 (2)	C9—N1—C11	121.0 (2)
C7—C8—S1	129.7 (2)	C10—S1—C8	92.50 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.93	2.57	3.442 (3)	157
C3—H3···O1ⁱ	0.93	2.55	3.407 (4)	154

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the University Sultan Moulay Slimane, Beni-Mellal, Morocco, for financial support.

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