Crystal structure of (Z)-3-allyl-5-(4-chloro­benzyl­idene)-2-sulfanyl­idene-1,3-thia­zolidin-4-one

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

doi:10.1107/S2056989015022689

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Page o1012

https://doi.org/10.1107/S2056989015022689

Open

access

Crystal structure of (Z)-3-allyl-5-(4-chlorobenzylidene)-2-sulfanylidene-1,3-thiazolidin-4-one

Rahhal El Ajlaoui,^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, Faculté des Sciences, Université Mohammed V de Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: r_elajlaoui@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 November 2015; accepted 26 November 2015; online 6 December 2015)

In the title compound, C₁₃H₁₀ClNOS₂, the dihedral angle between the rhodanine (r.m.s. deviation = 0.008 Å) and 4-chlorobenzylidene rings is 1.79 (11)°. The allyl group attached to the N atom, which lies almost perpendicular to the rhodanine ring, is disordered over two orientations in a 0.519 (13):0.481 (13) ratio. A short intramolecular C—H⋯S interaction closes an S(6) ring. In the crystal, molecules are linked by π–π stacking interactions [centroid–centroid separation = 3.600 (15) Å], generating inversion dimers.

Keywords: crystal structure; rhodanine-based molecules; pharmacological activity; biological activity; 1,3-thiazolidin-4-one.

CCDC reference: 1439050

1. Related literature

For a related structure and background to the pharmacological and biological activities of rhodanine-based molecules, see: El Ajlaoui et al. (2015 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₀ClNOS₂
M_r = 295.79
Triclinic, $[P \overline 1]$
a = 7.6197 (8) Å
b = 7.9849 (7) Å
c = 13.0624 (14) Å
α = 77.600 (5)°
β = 77.996 (5)°
γ = 61.954 (4)°
V = 679.76 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 296 K
0.37 × 0.25 × 0.21 mm

2.2. Data collection

Bruker X8 APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.656, T_max = 0.746
24189 measured reflections
3249 independent reflections
2199 reflections with I > 2σ(I)
R_int = 0.038

2.3. Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.144
S = 1.04
3249 reflections
182 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯S1	0.93	2.55	3.254 (3)	133

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1439050

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015022689/hb7551sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015022689/hb7551Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015022689/hb7551Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of rhodanine derivatives, we now describe the title compound.

The molecule of the title compound is build up from a rhodanine ring (S1–N1–C8–C9–C10) linked to an disordered allyl group (48%/52%) (C11–C12AC12B–C13AC13B) and at the nitrogen atom and to a 4-chlorobenzylidene ring system (C1 to C6) as shown in Fig.1. The mean plane through the rhodanine ring is almost perpendicular to the allyl group and makes a dihedral angle of 1.79 (11)° with the 4-chlorobenzylidene ring system. Nearly the same structure is observed by El Ajlaoui et al. 2015 in (Z)-3-Allyl-5-(4-methyl-benzylidene)-2- thioxothiazolidin-4-one.

The cohesion of the crystal structure is ensured by π—π interaction between molecules forming inversion dimers as shown in Fig.2.

Related literature top

For a related structure and background to the pharmacological and biological activities of rhodanine-based molecules, see: El Ajlaoui et al. (2015).

Experimental top

To a solution of 3-allylrhodanine (1.15 mmol, 0.2 g) in 10 mL of THF, (4-chlorobenzylidene)-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 Rf = 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 (Yield: 72%, m.p.: 371 K).

Structure description top

As part of our ongoing studies of rhodanine derivatives, we now describe the title compound.

The cohesion of the crystal structure is ensured by π—π interaction between molecules forming inversion dimers as shown in Fig.2.

For a related structure and background to the pharmacological and biological activities of rhodanine-based molecules, see: El Ajlaoui et al. (2015).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Plot of the molecule of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. Crystal packing for the title compound showing hydrogen bonds as dashed lines between inversion-related molecules.

(Z)-3-Allyl-5-(4-chlorobenzylidene)-2-sulfanylidene-1,3-thiazolidin-4-one top

Crystal data top

C₁₃H₁₀ClNOS₂	F(000) = 304
M_r = 295.79	D_x = 1.445 Mg m⁻³
Triclinic, P1	Melting point: 371 K
a = 7.6197 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9849 (7) Å	Cell parameters from 3249 reflections
c = 13.0624 (14) Å	θ = 2.9–27.9°
α = 77.600 (5)°	µ = 0.57 mm⁻¹
β = 77.996 (5)°	T = 296 K
γ = 61.954 (4)°	Block, colourless
V = 679.76 (12) Å³	0.37 × 0.25 × 0.21 mm
Z = 2

Data collection top

Bruker X8 APEX CCD diffractometer	3249 independent reflections
Radiation source: fine-focus sealed tube	2199 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
φ and ω scans	θ_max = 27.9°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→9
T_min = 0.656, T_max = 0.746	k = −10→10
24189 measured reflections	l = −17→17

Refinement top

Refinement on F²	3 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0576P)² + 0.2968P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3249 reflections	Δρ_max = 0.38 e Å⁻³
182 parameters	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₃H₁₀ClNOS₂	γ = 61.954 (4)°
M_r = 295.79	V = 679.76 (12) Å³
Triclinic, P1	Z = 2
a = 7.6197 (8) Å	Mo Kα radiation
b = 7.9849 (7) Å	µ = 0.57 mm⁻¹
c = 13.0624 (14) Å	T = 296 K
α = 77.600 (5)°	0.37 × 0.25 × 0.21 mm
β = 77.996 (5)°

Data collection top

Bruker X8 APEX CCD diffractometer	3249 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2199 reflections with I > 2σ(I)
T_min = 0.656, T_max = 0.746	R_int = 0.038
24189 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	3 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.04	Δρ_max = 0.38 e Å⁻³
3249 reflections	Δρ_min = −0.35 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	−0.1200 (4)	0.7895 (3)	0.6827 (2)	0.0698 (7)
C2	−0.0835 (4)	0.7296 (4)	0.5860 (2)	0.0709 (7)
H2	−0.1709	0.6939	0.5668	0.085*
C3	0.0823 (4)	0.7228 (3)	0.5181 (2)	0.0652 (6)
H3	0.1060	0.6822	0.4528	0.078*
C4	0.2174 (3)	0.7752 (3)	0.54439 (19)	0.0574 (6)
C5	0.1746 (4)	0.8355 (3)	0.6429 (2)	0.0678 (7)
H5	0.2612	0.8714	0.6627	0.081*
C6	0.0086 (5)	0.8438 (4)	0.7117 (2)	0.0762 (7)
H6	−0.0170	0.8853	0.7769	0.091*
C7	0.3946 (4)	0.7721 (3)	0.4765 (2)	0.0592 (6)
H4	0.4665	0.8149	0.5045	0.071*
C8	0.4733 (4)	0.7186 (3)	0.38062 (19)	0.0584 (6)
C9	0.6604 (4)	0.7264 (3)	0.3269 (2)	0.0634 (6)
C10	0.5892 (4)	0.6044 (4)	0.2013 (2)	0.0712 (7)
C11	0.8918 (5)	0.6605 (5)	0.1606 (3)	0.0912 (9)
H11A	0.9341	0.5757	0.1079	0.109*
H11B	1.0013	0.6194	0.2015	0.109*
C12A	0.8259 (17)	0.8701 (16)	0.1084 (6)	0.100 (3)	0.519 (13)
H12A	0.8190	0.9597	0.1463	0.120*	0.519 (13)
C13A	0.779 (2)	0.925 (2)	0.0099 (6)	0.131 (4)	0.519 (13)
H13A	0.7852	0.8369	−0.0287	0.157*	0.519 (13)
H13B	0.7393	1.0524	−0.0202	0.157*	0.519 (13)
C12B	0.8935 (18)	0.8039 (12)	0.0686 (7)	0.144 (6)	0.481 (13)
H12B	1.0008	0.7686	0.0151	0.172*	0.481 (13)
C13B	0.747 (2)	0.9822 (14)	0.0591 (12)	0.140 (6)	0.481 (13)
H13C	0.6384	1.0200	0.1117	0.168*	0.481 (13)
H13D	0.7530	1.0688	−0.0002	0.168*	0.481 (13)
N1	0.7137 (3)	0.6620 (3)	0.22888 (17)	0.0667 (5)
O1	0.7595 (3)	0.7794 (3)	0.36081 (16)	0.0818 (6)
S1	0.38675 (10)	0.63202 (10)	0.29984 (6)	0.0703 (2)
S2	0.61487 (17)	0.51989 (15)	0.09357 (7)	0.1047 (3)
Cl1	−0.33030 (13)	0.79962 (14)	0.76777 (7)	0.1017 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0656 (15)	0.0542 (13)	0.0814 (17)	−0.0180 (11)	−0.0213 (13)	−0.0017 (12)
C2	0.0635 (15)	0.0670 (15)	0.0856 (18)	−0.0260 (12)	−0.0248 (14)	−0.0091 (13)
C3	0.0675 (15)	0.0583 (13)	0.0731 (15)	−0.0225 (12)	−0.0262 (12)	−0.0119 (11)
C4	0.0618 (13)	0.0388 (10)	0.0715 (14)	−0.0163 (9)	−0.0270 (11)	−0.0041 (10)
C5	0.0759 (17)	0.0565 (13)	0.0795 (17)	−0.0280 (12)	−0.0257 (14)	−0.0138 (12)
C6	0.0841 (19)	0.0632 (15)	0.0758 (17)	−0.0217 (14)	−0.0203 (15)	−0.0153 (13)
C7	0.0652 (14)	0.0444 (11)	0.0755 (15)	−0.0228 (10)	−0.0310 (12)	−0.0052 (10)
C8	0.0647 (14)	0.0441 (11)	0.0727 (15)	−0.0224 (10)	−0.0320 (12)	−0.0019 (10)
C9	0.0704 (15)	0.0502 (12)	0.0743 (16)	−0.0265 (11)	−0.0300 (12)	0.0017 (11)
C10	0.0826 (17)	0.0618 (14)	0.0712 (16)	−0.0280 (13)	−0.0312 (14)	−0.0024 (12)
C11	0.094 (2)	0.101 (2)	0.082 (2)	−0.0513 (19)	−0.0114 (17)	−0.0002 (17)
C12A	0.118 (7)	0.113 (8)	0.074 (5)	−0.068 (7)	0.019 (5)	−0.014 (5)
C13A	0.134 (10)	0.109 (9)	0.136 (9)	−0.044 (8)	−0.018 (8)	−0.011 (7)
C12B	0.221 (15)	0.113 (8)	0.077 (7)	−0.075 (9)	0.033 (8)	−0.022 (6)
C13B	0.147 (9)	0.103 (8)	0.092 (9)	−0.008 (7)	0.022 (7)	−0.009 (6)
N1	0.0715 (13)	0.0601 (11)	0.0714 (13)	−0.0293 (10)	−0.0238 (11)	−0.0003 (10)
O1	0.0901 (13)	0.0898 (13)	0.0922 (13)	−0.0563 (11)	−0.0284 (11)	−0.0093 (10)
S1	0.0730 (4)	0.0733 (4)	0.0787 (4)	−0.0340 (3)	−0.0272 (3)	−0.0173 (3)
S2	0.1285 (8)	0.1284 (8)	0.0783 (5)	−0.0645 (6)	−0.0206 (5)	−0.0303 (5)
Cl1	0.0793 (5)	0.1100 (7)	0.1008 (6)	−0.0346 (5)	−0.0040 (4)	−0.0102 (5)

Geometric parameters (Å, º) top

C1—C2	1.374 (4)	C9—N1	1.392 (3)
C1—C6	1.384 (4)	C10—N1	1.366 (3)
C1—Cl1	1.728 (3)	C10—S2	1.626 (3)
C2—C3	1.370 (4)	C10—S1	1.749 (3)
C2—H2	0.9300	C11—N1	1.457 (4)
C3—C4	1.402 (3)	C11—C12B	1.4743 (10)
C3—H3	0.9300	C11—C12A	1.543 (11)
C4—C5	1.392 (3)	C11—H11A	0.9700
C4—C7	1.445 (4)	C11—H11B	0.9700
C5—C6	1.373 (4)	C12A—C13A	1.3334 (10)
C5—H5	0.9300	C12A—H12A	0.9300
C6—H6	0.9300	C13A—H13A	0.9300
C7—C8	1.338 (3)	C13A—H13B	0.9300
C7—H4	0.9300	C12B—C13B	1.3333 (10)
C8—C9	1.475 (4)	C12B—H12B	0.9300
C8—S1	1.749 (2)	C13B—H13C	0.9300
C9—O1	1.211 (3)	C13B—H13D	0.9300

C2—C1—C6	120.6 (3)	N1—C10—S2	127.3 (2)
C2—C1—Cl1	119.4 (2)	N1—C10—S1	110.9 (2)
C6—C1—Cl1	119.9 (2)	S2—C10—S1	121.89 (17)
C3—C2—C1	119.5 (2)	N1—C11—C12B	125.5 (5)
C3—C2—H2	120.2	N1—C11—C12A	104.4 (5)
C1—C2—H2	120.2	N1—C11—H11A	110.9
C2—C3—C4	121.8 (2)	C12A—C11—H11A	110.9
C2—C3—H3	119.1	N1—C11—H11B	110.9
C4—C3—H3	119.1	C12A—C11—H11B	110.9
C5—C4—C3	116.8 (2)	H11A—C11—H11B	108.9
C5—C4—C7	118.5 (2)	C13A—C12A—C11	121.3 (11)
C3—C4—C7	124.7 (2)	C13A—C12A—H12A	119.4
C6—C5—C4	122.1 (2)	C11—C12A—H12A	119.4
C6—C5—H5	119.0	C12A—C13A—H13A	120.0
C4—C5—H5	119.0	C12A—C13A—H13B	120.0
C5—C6—C1	119.1 (3)	H13A—C13A—H13B	120.0
C5—C6—H6	120.4	C13B—C12B—C11	122.4 (11)
C1—C6—H6	120.4	C13B—C12B—H12B	118.8
C8—C7—C4	131.4 (2)	C11—C12B—H12B	118.8
C8—C7—H4	114.3	C12B—C13B—H13C	120.0
C4—C7—H4	114.3	C12B—C13B—H13D	120.0
C7—C8—C9	121.4 (2)	H13C—C13B—H13D	120.0
C7—C8—S1	129.3 (2)	C10—N1—C9	116.3 (2)
C9—C8—S1	109.29 (18)	C10—N1—C11	123.1 (3)
O1—C9—N1	122.6 (3)	C9—N1—C11	120.6 (2)
O1—C9—C8	126.4 (3)	C8—S1—C10	92.62 (12)
N1—C9—C8	110.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1	0.93	2.55	3.254 (3)	133

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···S1	0.93	2.55	3.254 (3)	133

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.

References

Bruker (2009). APEX2, SAINT and SADABS. 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
El Ajlaoui, R., Rakib, E. M., Chigr, M., Saadi, M. & El Ammari, L. (2015). Acta Cryst. E71, o906–o907. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Page o1012

https://doi.org/10.1107/S2056989015022689

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Crystal structure of (Z)-3-allyl-5-(4-chloro­benzyl­­idene)-2-sulfanyl­­idene-1,3-thia­zolidin-4-one

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (Z)-3-allyl-5-(4-chlorobenzylidene)-2-sulfanylidene-1,3-thiazolidin-4-one