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

Rahhal El Ajlaoui; El Mostapha Rakib; Issam Forsal; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S2056989015022884

. 2015 Dec 6;71(Pt 12):o1010–o1011. doi: 10.1107/S2056989015022884

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

Rahhal El Ajlaoui ^a,^*, El Mostapha Rakib ^a, Issam Forsal ^a, Mohamed Saadi ^b, Lahcen El Ammari ^b

PMCID: PMC4719950 PMID: 26870469

Abstract

In the title compound, C₁₃H₁₀BrNOS₂, the rhodanine (systematic name: 2-sulfanylidene-1,3-thiazolidin-4-one) and the 3-bromobenzylidene ring systems are inclined slightly, forming a dihedral angle of 5.86 (12)°. The rhodanine moiety is linked to an allyl group at the N atom and to the 3-bromobenzylidene ring system. The allyl group, C=C—C, is nearly perpendicular to the mean plane through the rhodanine ring, maling a dihedral angle of 87.2 (5)°. In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R ₂ ²(10) ring motif.

Keywords: crystal structure, rhodanine, hydrogen bonding

Related literature

For pharmacological and biological activities of rhodanine-based molecules, see: Tomasić & Masic (2009 ▸); Sortino et al. (2007 ▸); Kesel (2003 ▸); Capan et al. (1996 ▸); Momose et al. (1991 ▸); Kawakami et al. (1998 ▸); Insuasty et al. (2010 ▸). For the crystal structure of a related compound, see: El Ajlaoui et al. (2015 ▸).

Experimental

Crystal data

C₁₃H₁₀BrNOS₂
M _r = 340.25
Triclinic,
a = 5.4044 (6) Å
b = 11.2306 (13) Å
c = 11.7966 (13) Å
α = 80.100 (5)°
β = 84.912 (6)°
γ = 76.732 (6)°
V = 685.60 (13) Å³
Z = 2
Mo Kα radiation
μ = 3.29 mm⁻¹
T = 296 K
0.31 × 0.27 × 0.21 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.479, T _max = 0.746
25482 measured reflections
4181 independent reflections
2895 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.098
S = 1.01
4181 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015022884/su5249sup1.cif

e-71-o1010-sup1.cif^{(785.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022884/su5249Isup2.hkl

e-71-o1010-Isup2.hkl^{(333.1KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015022884/su5249Isup3.cml

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

. DOI: 10.1107/S2056989015022884/su5249fig1.tif

A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.5MB, tif)}

a . DOI: 10.1107/S2056989015022884/su5249fig2.tif

A view along the a axis of the crystal packing of the title compound, showing the hydrogen bonds as dashed lines (see Table 1).

CCDC reference: 1439611

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.93	2.42	3.310 (3)	159

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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. Structural commentary

Rhodanine is an attractive scaffold unit because of its prestigious position in medicinal chemistry as it is responsible for numerous pharmacological and biological activities (Tomasic & Masic, 2009), e.g., antimicrobial, antiviral, anticonvulsant, antidiabetic and antitumor activities (Sortino et al., 2007; Kesel, 2003; Capan et al., 1996; Momose et al., 1991; Kawakami et al., 1998; Insuasty et al. 2010). The unusual biological activity displayed by many rhodanine-based molecules have made them attractive synthetic targets.

The title compound, Fig. 1, is build up from a rhodanine ring (S1/N/1 C8–C10) linked to an allyl group (C11–C13) at the nitrogen atom and to a 3-bromobenzylidene ring system (C1—C6). The mean plane through the rhodanine ring is almost perpendicular to the allyl group (C11—C13) with a dihedral angle of 87.2 (5) °, and makes a dihedral angle of 5.86 (12)° with the 3-bromobenzylidene ring. A very similar arrangement has been observed in the crystal structure of (Z)-3-allyl-5-(4-methyl-benzylidene)-2-thioxothiazolidin-4-one, but with disorder in the allyl group (El Ajlaoui et al., 2015).

In the crystal, molecules are linked by a pair of C—H···O hydrogen bonds forming inversion dimers with an R²₂(10) ring motif (Table 1 and Fig. 2).

S2. Synthesis and crystallization

To a solution of 3-allylrhodanine (1.15 mmol, 0.2 g) in 10 ml of THF, (3-bromobenzylidene)-4-methyl-5-oxopyrazolidin-2-ium-1-ide (1.38 mmol) was added and the mixture refluxed for 8 h, monitored by TLC. On completion of the reaction, with a yellow spot (TLC Rf = 0.3, using hexane/ethyl acetate 1:9) 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 giving colourless block-like crystals (yield: 76%; m.p. 390 K).

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were located in a difference Fourier map and treated as riding: C–H = 0.93–0.97 Å with U_iso(H) = 1.2U_eq(C). Two reflections, (0 1 0) and (0 0 1), affected by the beam-stop were removed during the final cycles of refinement.