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

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

doi:10.1107/S2056989015010166

organic compounds

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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 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, Avenue Ibn Battouta, BP. 1014, Rabat, Morocco
^*Correspondence e-mail: r_elajlaoui@yahoo.fr

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 20 May 2015; accepted 26 May 2015; online 30 May 2015)

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.

CCDC reference: 1403058

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₁H₉NOS₃
M_r = 267.37
Triclinic, $[P \overline 1]$
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.54	3.304 (3)	140
Symmetry code: (i) -x+2, -y, -z+1.

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 ).

Supporting information

CCDC reference: 1403058

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

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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).

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: 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).

Figures top

	Fig. 1. 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.
	Fig. 2. Partial crystal packing of the title compound showing hydrogen bonds and π–π interactions between molecules.

(E)-3-Allyl-2-sulfanylidene-5-[(thiophen-2-yl)methylidene]thiazolidin-4-one top

Crystal data top

C₁₁H₉NOS₃	Z = 2
M_r = 267.37	F(000) = 276
Triclinic, P1	D_x = 1.476 Mg m⁻³
a = 6.7342 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.3762 (2) Å	Cell parameters from 3514 reflections
c = 13.2917 (5) Å	θ = 3.0–30.0°
α = 79.386 (2)°	µ = 0.59 mm⁻¹
β = 80.104 (2)°	T = 296 K
γ = 68.908 (1)°	Block, yellow
V = 601.44 (3) Å³	0.37 × 0.35 × 0.28 mm

Data collection top

Bruker X8 APEX diffractometer	3514 independent reflections
Radiation source: fine-focus sealed tube	2557 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ϕ and ω scans	θ_max = 30.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.700, T_max = 0.746	k = −10→10
25223 measured reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0384P)² + 0.3716P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3514 reflections	Δρ_max = 0.35 e Å⁻³
145 parameters	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₉NOS₃	γ = 68.908 (1)°
M_r = 267.37	V = 601.44 (3) Å³
Triclinic, P1	Z = 2
a = 6.7342 (2) Å	Mo Kα radiation
b = 7.3762 (2) Å	µ = 0.59 mm⁻¹
c = 13.2917 (5) Å	T = 296 K
α = 79.386 (2)°	0.37 × 0.35 × 0.28 mm
β = 80.104 (2)°

Data collection top

Bruker X8 APEX diffractometer	3514 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2557 reflections with I > 2σ(I)
T_min = 0.700, T_max = 0.746	R_int = 0.042
25223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.07	Δρ_max = 0.35 e Å⁻³
3514 reflections	Δρ_min = −0.26 e Å⁻³
145 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.

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

	x	y	z	U_iso*/U_eq
C1	0.1345 (4)	0.1860 (4)	0.70306 (19)	0.0518 (6)
H1	−0.0046	0.2033	0.7342	0.062*
C2	0.3105 (4)	0.0861 (4)	0.75114 (18)	0.0523 (6)
H2	0.3058	0.0267	0.8192	0.063*
C3	0.5018 (4)	0.0808 (3)	0.68783 (17)	0.0428 (5)
H3	0.6372	0.0182	0.7094	0.051*
C4	0.4669 (3)	0.1785 (3)	0.59025 (16)	0.0350 (4)
C5	0.6327 (3)	0.1940 (3)	0.50925 (16)	0.0358 (4)
H5	0.7718	0.1321	0.5264	0.043*
C6	0.6167 (3)	0.2849 (3)	0.41203 (16)	0.0341 (4)
C7	0.8086 (3)	0.2828 (3)	0.33909 (16)	0.0366 (4)
C8	0.5339 (3)	0.4692 (3)	0.23605 (17)	0.0399 (5)
C9	0.9117 (4)	0.4146 (4)	0.15934 (19)	0.0491 (6)
H9A	0.8550	0.5408	0.1181	0.059*
H9B	1.0355	0.4141	0.1876	0.059*
C10	0.9801 (6)	0.2599 (5)	0.0927 (2)	0.0743 (9)
H10	0.8740	0.2392	0.0646	0.089*
C11	1.1737 (7)	0.1513 (6)	0.0701 (3)	0.1111 (16)
H11A	1.2845	0.1674	0.0967	0.133*
H11B	1.2038	0.0562	0.0272	0.133*
N1	0.7483 (3)	0.3913 (3)	0.24437 (13)	0.0382 (4)
O1	0.9933 (2)	0.2023 (3)	0.35541 (13)	0.0515 (4)
S1	0.19548 (9)	0.27676 (9)	0.57905 (5)	0.04606 (16)
S2	0.38596 (8)	0.41472 (8)	0.35129 (4)	0.03895 (14)
S3	0.41977 (12)	0.59688 (12)	0.13403 (5)	0.0646 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0437 (13)	0.0519 (14)	0.0552 (15)	−0.0171 (11)	0.0135 (11)	−0.0117 (11)
C2	0.0583 (15)	0.0566 (14)	0.0374 (12)	−0.0213 (12)	0.0061 (11)	−0.0020 (10)
C3	0.0425 (12)	0.0437 (12)	0.0389 (11)	−0.0123 (10)	−0.0042 (9)	−0.0028 (9)
C4	0.0343 (10)	0.0315 (10)	0.0392 (11)	−0.0108 (8)	−0.0029 (8)	−0.0065 (8)
C5	0.0316 (10)	0.0343 (10)	0.0406 (11)	−0.0101 (8)	−0.0032 (8)	−0.0054 (8)
C6	0.0304 (9)	0.0340 (10)	0.0377 (10)	−0.0111 (8)	−0.0022 (8)	−0.0060 (8)
C7	0.0337 (10)	0.0393 (11)	0.0389 (11)	−0.0156 (9)	−0.0002 (8)	−0.0077 (9)
C8	0.0402 (11)	0.0412 (11)	0.0394 (11)	−0.0151 (9)	−0.0030 (9)	−0.0063 (9)
C9	0.0447 (13)	0.0555 (14)	0.0469 (13)	−0.0242 (11)	0.0066 (10)	−0.0024 (10)
C10	0.084 (2)	0.086 (2)	0.0568 (17)	−0.0438 (19)	0.0266 (15)	−0.0216 (15)
C11	0.133 (4)	0.086 (3)	0.067 (2)	0.002 (2)	0.025 (2)	−0.0083 (19)
N1	0.0360 (9)	0.0424 (9)	0.0370 (9)	−0.0165 (8)	0.0006 (7)	−0.0051 (7)
O1	0.0298 (8)	0.0662 (11)	0.0532 (10)	−0.0130 (7)	−0.0035 (7)	−0.0032 (8)
S1	0.0340 (3)	0.0453 (3)	0.0515 (3)	−0.0083 (2)	−0.0008 (2)	−0.0031 (2)
S2	0.0291 (2)	0.0432 (3)	0.0410 (3)	−0.0101 (2)	−0.0029 (2)	−0.0024 (2)
S3	0.0557 (4)	0.0842 (5)	0.0448 (4)	−0.0184 (4)	−0.0133 (3)	0.0101 (3)

Geometric parameters (Å, º) top

C1—C2	1.347 (4)	C7—O1	1.208 (2)
C1—S1	1.701 (3)	C7—N1	1.400 (3)
C1—H1	0.9300	C8—N1	1.364 (3)
C2—C3	1.405 (3)	C8—S3	1.638 (2)
C2—H2	0.9300	C8—S2	1.743 (2)
C3—C4	1.377 (3)	C9—C10	1.468 (4)
C3—H3	0.9300	C9—N1	1.468 (3)
C4—C5	1.433 (3)	C9—H9A	0.9700
C4—S1	1.729 (2)	C9—H9B	0.9700
C5—C6	1.344 (3)	C10—C11	1.278 (5)
C5—H5	0.9300	C10—H10	0.9300
C6—C7	1.473 (3)	C11—H11A	0.9300
C6—S2	1.749 (2)	C11—H11B	0.9300

C2—C1—S1	112.36 (18)	N1—C8—S3	126.87 (17)
C2—C1—H1	123.8	N1—C8—S2	110.96 (16)
S1—C1—H1	123.8	S3—C8—S2	122.17 (13)
C1—C2—C3	113.0 (2)	C10—C9—N1	113.0 (2)
C1—C2—H2	123.5	C10—C9—H9A	109.0
C3—C2—H2	123.5	N1—C9—H9A	109.0
C4—C3—C2	112.6 (2)	C10—C9—H9B	109.0
C4—C3—H3	123.7	N1—C9—H9B	109.0
C2—C3—H3	123.7	H9A—C9—H9B	107.8
C3—C4—C5	124.61 (19)	C11—C10—C9	125.3 (4)
C3—C4—S1	110.43 (16)	C11—C10—H10	117.4
C5—C4—S1	124.96 (16)	C9—C10—H10	117.4
C6—C5—C4	129.47 (19)	C10—C11—H11A	120.0
C6—C5—H5	115.3	C10—C11—H11B	120.0
C4—C5—H5	115.3	H11A—C11—H11B	120.0
C5—C6—C7	121.35 (19)	C8—N1—C7	116.63 (17)
C5—C6—S2	128.78 (16)	C8—N1—C9	122.99 (19)
C7—C6—S2	109.86 (15)	C7—N1—C9	120.37 (18)
O1—C7—N1	123.06 (19)	C1—S1—C4	91.64 (11)
O1—C7—C6	126.9 (2)	C8—S2—C6	92.49 (10)
N1—C7—C6	110.02 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.54	3.304 (3)	140

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.54	3.304 (3)	139.7

Symmetry code: (i) −x+2, −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.

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
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hu, Y., Helm, J. S., Chen, L., Ginsberg, C., Gross, B., Kraybill, B., Tiyanont, K., Fang, X., Wu, T. & Walker, S. (2004). Chem. Biol. 11, 703–711. PubMed CAS Google Scholar
Insuasty, B., Gutie'rrez, A., Quiroga, J., Abonia, R., Nogueras, M., Cobo, J., Svetaz, L., Raimondi, M. & Zacchino, S. (2010). Arch. Pharm. 343, 48–53. CAS Google Scholar
Johnson, A. R., Marletta, M. A. & Dyer, R. D. (2001). Biochemistry, 40, 7736–7745. CrossRef PubMed CAS Google Scholar
Nasr, M. N. A. & Said, S. A. (2003). Arch. Pharm. Pharm. Med. Chem. 336, 551–559. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Soltero-Higgin, M., Carlson, E. E., Phillips, J. H. & Kiessling, L. L. (2004). J. Am. Chem. Soc. 126, 10532–10533. PubMed CAS Google Scholar
Sortino, M., Delgado, P., Juárez, S., Quiroga, J., Abonía, R., Insuasty, B., Nogueras, M., Rodero, L., Garibotto, F. M., Enriz, R. D. & Zacchino, S. A. (2007). Bioorg. Med. Chem. 15, 484–494. PubMed CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tomasić, T. & Masic, L. P. (2009). Curr. Med. Chem. 16, 1596–1629. PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages o433-o434

doi:10.1107/S2056989015010166

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

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