Crystal structure of (E)-3-allyl-2-sulfanyl­idene-5-[(thio­phen-2-yl)methyl­idene]thia­zolidin-4-one

Rahhal El Ajlaoui; El Mostapha Rakib; Souad Mojahidi; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S2056989015010166

. 2015 May 30;71(Pt 6):o433–o434. doi: 10.1107/S2056989015010166

Crystal structure of (E)-3-allyl-2-sulfanylidene-5-[(thiophen-2-yl)methylidene]thiazolidin-4-one

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

PMCID: PMC4459307 PMID: 26090212

Abstract

Molecules of the title compound, C₁₁H₉NOS₃, are built up by one thiophene and one 2-thioxathiazolidin-4-one ring which are connected by a methylene bridge. In addition, there is an allyl substituent attached to nitrogen. The two rings are almost coplanar, making a dihedral angle between them of 0.76 (11)°. The allyl group is oriented perpendicular to the mean plane through both ring systems. The crystal structure exhibits inversion dimers in which molecules are linked by pairs of C—H⋯O hydrogen bonds. Additional π–π interactions between neighboring thiophene and 2-thioxathiazolidin-4-one rings [intercentroid distance = 3.694 (2) Å] lead to the formation of a three-dimensional network.

Keywords: crystal structure, rhodanine derivative, 2-thioxathiazolidin-4-one, hydrogen bonding, π–π interactions

Related literature

For pharmacological activities such as antimicrobial and anti-inflammatory of arylidene derivatives of rhodanine (2-thioxo-1,3-thiazolidin-4-one), see: Soltero-Higgin et al. (2004 ▸); Hu et al. (2004 ▸); Nasr & Said (2003 ▸); Johnson et al. (2001 ▸); Sortino et al. (2007 ▸); Insuasty et al. (2010 ▸); Tomasic & Masic (2009 ▸).

Experimental

Crystal data

C₁₁H₉NOS₃
M _r = 267.37
Triclinic,
a = 6.7342 (2) Å
b = 7.3762 (2) Å
c = 13.2917 (5) Å
α = 79.386 (2)°
β = 80.104 (2)°
γ = 68.908 (1)°
V = 601.44 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 296 K
0.37 × 0.35 × 0.28 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.700, T _max = 0.746
25223 measured reflections
3514 independent reflections
2557 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.111
S = 1.07
3514 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

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: SHELXL97 (Sheldrick, 2008 ▸); 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 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015010166/im2466sup1.cif

e-71-0o433-sup1.cif^{(733.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010166/im2466Isup2.hkl

e-71-0o433-Isup2.hkl^{(280.3KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015010166/im2466Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015010166/im2466fig1.tif

Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles of arbitrary radius.

Click here for additional data file.^{(2.2MB, tif)}

. DOI: 10.1107/S2056989015010166/im2466fig2.tif

Partial crystal packing of the title compound showing hydrogen bonds and π–π interactions between molecules.

CCDC reference: 1403058

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C3H3O1ⁱ	0.93	2.54	3.304(3)	140

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Symmetry code: (i) Inline graphic .

Acknowledgments

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.

supplementary crystallographic information

S1. Comment

Rhodanine (2-thioxo-1,3-thiazolidin-4-one) is the key structural feature of a very important group of heterocyclic compounds for drug discovery programs. Arylidene derivatives of rhodanine have attracted great interest for synthetic organic chemists due to the broad biological activities of this class of compounds including antimicrobial (Sortino et al.; 2007, Hu et al., 2004), anti-inflammatory (Nasr & Said, 2003; Johnson et al. 2001), and antifungal (Sortino et al., 2007; Insuasty et al., 2010) properties. Additionally, rhodanine derivatives may potentially be used in the treatment of diabetes, obesity, Alzheimer's disease, cystic fibrosis, thrombocytopenia, cancer, sleep, mood and central nervous system disorders as well as chronic inflammation (Tomasic & Masic, 2009).

The two five-membered rings (C1–C4, S1 and C6– C8, N1, S2) forming the molecule are almost coplanar, with a maximum deviation of -0.023 (2) Å for C7 (Fig.1). The allyl group is oriented perpendicular to the mean plane through the thioxothiazolidine cycle as indicated by the torsion angle C10–C9–N1–C7 of 90.2 (3)°.

The cohesion of the crystal structure is ensured by C3–H3···O1 hydrogen bonds between molecules forming a dimers and π–π interactions between heterocycles [intercentroid distance = 3.69 (2) Å], forming a three-dimensional network as shown in Fig.2 and Table 1.

S2. Experimental

To a solution of 3-allyl-2-thioxo-1,3-thiazolidin-4-one (1.15 mmol, 0.2 g) in 10 ml of THF methyl-2-(thiophen-2-ylmethylene)-5-oxopyrazolidin-2-ium-1-ide (1.38 mmol) was added. The mixture was refluxed for 8 h and was monitored by TLC. After the reaction was completed only one yellow spot (TLC R_f = 0.3, hexane/ethyl acetate 1:9) was generated cleanly. The solvent was evaporated in vacuo. The crude product was purified on silica using hexane: ethyl acetate (1/9) as eluent. The product was obtained as a yellow crystal solid (Yield: 55%, m.p.: 403 K).