organic compounds
(Z)-3-Allyl-5-(3-methoxybenzylidene)-2-sulfanylidene-1,3-thiazolidin-4-one
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
In the title compound, C14H13NO2S2, the rhodanine ring and the 3-methoxybenzylidene ring are nearly coplanar, as indicated by the dihedral angle of 1.77 (6)° between their planes. The allyl group is nearly perpendicular to the rhodanine ring, with a dihedral angle of 83.64 (19)°. An intramolecular C—H⋯S interaction forms an S(6) ring motif. In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds into inversion dimers.
Keywords: crystal structure; rhodanine-based molecule; hydrogen bonds.
CCDC reference: 1446566
Structure description
Compounds containing 2-thioxothiazolidin-4-one (rhodanine) and its derivatives have been reported to exhibit a broad spectrum of biological activities, acting as antidiabetic, anticancer, antitubercular, anti-HIV and antiparasitic agents (Murugan et al., 2009; Chandrappa et al., 2009; Mallikarjuna et al., 2009; Murugesan et al., 2011; Zhang et al., 2009). The unusual biological activity displayed by many rhodanine-based molecules has made them attractive synthetic targets.
The molecule of the title compound is build up from a rhodanine ring (S1/N1/C8–C10) linked to an allyl group (C11–C13) at the nitrogen atom and to a 3-methoxybenzylidene ring (C1–C6) as shown in Fig. 1. In the crystal, molecules are linked by pairs of C—H⋯O hydrogen bonds (Table 1), forming an inversion dimer as shown in Fig. 2.
Synthesis and crystallization
To a solution of 3-allylrhodanine (1.15 mmol, 0.2 g) in 10 ml of THF, (3-methoxybenzylidene)-4-methyl-5-oxopyrazolidin-2-ium-1-ide (1.38 mmol) was added. The mixture was refluxed for 8 h until the reaction was completed (TLC) 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 The title compound was recrystallized from ethanol (yield 78%, m.p. 364 K).
Refinement
Crystal data, data collection and structure . The reflection (0 0 1) was affected by the beam-stop and was removed during refinement.
details are summarized in Table 2Structural data
CCDC reference: 1446566
10.1107/S2414314616000523/is4001sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616000523/is4001Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616000523/is4001Isup3.cml
To a solution of 3-allylrhodanine (1.15 mmol, 0.2 g) in 10 ml of THF, (3-methoxybenzylidene)-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
The title compound was recrystallized from ethanol (yield 78%, m.p. 364 K).Crystal data, data collection and structure
details are summarized in Table 2. The reflection (0 0 1) affected by the beam-stop was removed during refinement.Compounds containing 2-thioxothiazolidin-4-one (rhodanine) and its derivatives have been reported to exhibit a broad spectrum of biological activities, acting as antidiabetic, anticancer, antitubercular, anti-HIV and antiparasitic agents (Murugan et al., 2009; Chandrappa et al., 2009; Mallikarjuna et al., 2009; Murugesan et al., 2011; Zhang et al., 2009). The unusual biological activity displayed by many rhodanine-based molecules has made them attractive synthetic targets.
The molecule of the title compound is build up from a rhodanine ring (S1/N1/C8–C10) linked to an allyl group (C11–C13) at the nitrogen atom and to a 3-methoxybenzylidene ring (C1–C6) as shown in Fig. 1. In the crystal, molecules are linked by pairs of C—H···O hydrogen bonds (Table 1), forming an inversion dimer as shown in Fig. 2.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure 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. | |
Fig. 2. A crystal packing diagram of the title compound, showing the hydrogen bonds as dashed lines. |
C14H13NO2S2 | F(000) = 304 |
Mr = 291.37 | Dx = 1.380 Mg m−3 |
Triclinic, P1 | Melting point: 364 K |
a = 6.9841 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.3241 (18) Å | Cell parameters from 4522 reflections |
c = 13.116 (3) Å | θ = 2.6–31.2° |
α = 89.276 (9)° | µ = 0.38 mm−1 |
β = 75.614 (9)° | T = 296 K |
γ = 72.095 (10)° | Block, colourless |
V = 701.2 (3) Å3 | 0.31 × 0.27 × 0.21 mm |
Z = 2 |
Bruker X8 APEX diffractometer | 4522 independent reflections |
Radiation source: fine-focus sealed tube | 3618 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 31.2°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.479, Tmax = 0.746 | k = −12→12 |
28065 measured reflections | l = −19→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0624P)2 + 0.1273P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
4522 reflections | Δρmax = 0.30 e Å−3 |
172 parameters | Δρmin = −0.26 e Å−3 |
C14H13NO2S2 | γ = 72.095 (10)° |
Mr = 291.37 | V = 701.2 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9841 (14) Å | Mo Kα radiation |
b = 8.3241 (18) Å | µ = 0.38 mm−1 |
c = 13.116 (3) Å | T = 296 K |
α = 89.276 (9)° | 0.31 × 0.27 × 0.21 mm |
β = 75.614 (9)° |
Bruker X8 APEX diffractometer | 4522 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3618 reflections with I > 2σ(I) |
Tmin = 0.479, Tmax = 0.746 | Rint = 0.029 |
28065 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.30 e Å−3 |
4522 reflections | Δρmin = −0.26 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6784 (2) | 0.92899 (16) | 0.26792 (11) | 0.0453 (3) | |
C2 | 0.8814 (2) | 0.88347 (19) | 0.27837 (12) | 0.0528 (3) | |
H2 | 0.9846 | 0.9093 | 0.2274 | 0.063* | |
C3 | 0.9283 (2) | 0.8002 (2) | 0.36440 (12) | 0.0555 (3) | |
H3 | 1.0641 | 0.7700 | 0.3711 | 0.067* | |
C4 | 0.7776 (2) | 0.76011 (19) | 0.44141 (11) | 0.0512 (3) | |
H4 | 0.8122 | 0.7042 | 0.4993 | 0.061* | |
C5 | 0.57287 (19) | 0.80427 (16) | 0.43169 (10) | 0.0410 (2) | |
C6 | 0.52494 (19) | 0.88990 (16) | 0.34378 (10) | 0.0418 (3) | |
H6 | 0.3895 | 0.9205 | 0.3365 | 0.050* | |
C7 | 0.40267 (19) | 0.76903 (16) | 0.50824 (10) | 0.0431 (3) | |
H7 | 0.2737 | 0.8106 | 0.4932 | 0.052* | |
C8 | 0.40122 (19) | 0.68638 (16) | 0.59698 (10) | 0.0408 (2) | |
C9 | 0.2049 (2) | 0.66565 (17) | 0.66206 (10) | 0.0450 (3) | |
C10 | 0.4403 (2) | 0.52824 (16) | 0.76057 (10) | 0.0434 (3) | |
C11 | 0.0714 (2) | 0.53236 (19) | 0.82335 (12) | 0.0520 (3) | |
H11A | 0.1286 | 0.4223 | 0.8486 | 0.062* | |
H11B | −0.0273 | 0.5227 | 0.7851 | 0.062* | |
C12 | −0.0422 (2) | 0.65574 (19) | 0.91596 (12) | 0.0533 (3) | |
H12 | −0.1612 | 0.6390 | 0.9590 | 0.064* | |
C13 | 0.0068 (3) | 0.7842 (2) | 0.94329 (14) | 0.0677 (4) | |
H13A | 0.1244 | 0.8067 | 0.9030 | 0.081* | |
H13B | −0.0757 | 0.8538 | 1.0031 | 0.081* | |
C14 | 0.4469 (3) | 1.0541 (2) | 0.16012 (13) | 0.0616 (4) | |
H14A | 0.4481 | 1.1117 | 0.0962 | 0.092* | |
H14B | 0.4124 | 0.9525 | 0.1529 | 0.092* | |
H14C | 0.3452 | 1.1265 | 0.2178 | 0.092* | |
N1 | 0.24062 (17) | 0.57615 (14) | 0.75017 (9) | 0.0435 (2) | |
O1 | 0.03559 (17) | 0.71622 (17) | 0.64424 (9) | 0.0660 (3) | |
O2 | 0.64706 (17) | 1.01213 (16) | 0.18002 (9) | 0.0643 (3) | |
S1 | 0.60384 (5) | 0.59150 (4) | 0.65517 (3) | 0.04671 (11) | |
S2 | 0.52699 (7) | 0.42768 (6) | 0.85588 (3) | 0.06213 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0380 (6) | 0.0469 (6) | 0.0453 (6) | −0.0068 (5) | −0.0083 (5) | −0.0009 (5) |
C2 | 0.0346 (6) | 0.0607 (8) | 0.0560 (8) | −0.0105 (5) | −0.0042 (5) | −0.0015 (6) |
C3 | 0.0317 (6) | 0.0695 (9) | 0.0612 (9) | −0.0085 (6) | −0.0135 (6) | −0.0020 (7) |
C4 | 0.0391 (6) | 0.0636 (8) | 0.0488 (7) | −0.0090 (6) | −0.0162 (5) | 0.0004 (6) |
C5 | 0.0352 (5) | 0.0458 (6) | 0.0395 (6) | −0.0076 (4) | −0.0110 (4) | −0.0062 (5) |
C6 | 0.0332 (5) | 0.0470 (6) | 0.0422 (6) | −0.0077 (4) | −0.0100 (4) | −0.0035 (5) |
C7 | 0.0354 (5) | 0.0534 (7) | 0.0409 (6) | −0.0113 (5) | −0.0135 (5) | −0.0028 (5) |
C8 | 0.0349 (5) | 0.0488 (6) | 0.0392 (6) | −0.0105 (5) | −0.0132 (4) | −0.0048 (5) |
C9 | 0.0406 (6) | 0.0549 (7) | 0.0441 (6) | −0.0171 (5) | −0.0166 (5) | 0.0017 (5) |
C10 | 0.0416 (6) | 0.0445 (6) | 0.0449 (6) | −0.0107 (5) | −0.0161 (5) | −0.0023 (5) |
C11 | 0.0508 (7) | 0.0571 (8) | 0.0593 (8) | −0.0288 (6) | −0.0195 (6) | 0.0116 (6) |
C12 | 0.0428 (7) | 0.0607 (8) | 0.0539 (8) | −0.0159 (6) | −0.0095 (6) | 0.0197 (6) |
C13 | 0.0682 (10) | 0.0646 (9) | 0.0590 (9) | −0.0200 (8) | 0.0030 (8) | −0.0032 (7) |
C14 | 0.0578 (9) | 0.0692 (9) | 0.0569 (9) | −0.0132 (7) | −0.0219 (7) | 0.0129 (7) |
N1 | 0.0412 (5) | 0.0495 (6) | 0.0440 (5) | −0.0169 (4) | −0.0150 (4) | 0.0016 (4) |
O1 | 0.0423 (5) | 0.0990 (9) | 0.0671 (7) | −0.0278 (5) | −0.0264 (5) | 0.0233 (6) |
O2 | 0.0462 (6) | 0.0820 (8) | 0.0585 (6) | −0.0147 (5) | −0.0103 (5) | 0.0227 (6) |
S1 | 0.03460 (15) | 0.0597 (2) | 0.04389 (18) | −0.00911 (13) | −0.01372 (12) | 0.00062 (13) |
S2 | 0.0570 (2) | 0.0726 (3) | 0.0594 (2) | −0.01587 (19) | −0.02600 (18) | 0.01825 (18) |
C1—O2 | 1.3668 (17) | C9—N1 | 1.4001 (17) |
C1—C6 | 1.3860 (18) | C10—N1 | 1.3685 (17) |
C1—C2 | 1.3920 (19) | C10—S2 | 1.6335 (14) |
C2—C3 | 1.373 (2) | C10—S1 | 1.7494 (14) |
C2—H2 | 0.9300 | C11—N1 | 1.4639 (17) |
C3—C4 | 1.385 (2) | C11—C12 | 1.487 (2) |
C3—H3 | 0.9300 | C11—H11A | 0.9700 |
C4—C5 | 1.4008 (18) | C11—H11B | 0.9700 |
C4—H4 | 0.9300 | C12—C13 | 1.298 (2) |
C5—C6 | 1.4050 (18) | C12—H12 | 0.9300 |
C5—C7 | 1.4564 (18) | C13—H13A | 0.9300 |
C6—H6 | 0.9300 | C13—H13B | 0.9300 |
C7—C8 | 1.3441 (19) | C14—O2 | 1.422 (2) |
C7—H7 | 0.9300 | C14—H14A | 0.9600 |
C8—C9 | 1.4827 (18) | C14—H14B | 0.9600 |
C8—S1 | 1.7445 (13) | C14—H14C | 0.9600 |
C9—O1 | 1.2079 (16) | ||
O2—C1—C6 | 124.67 (12) | N1—C10—S2 | 127.52 (11) |
O2—C1—C2 | 115.21 (13) | N1—C10—S1 | 110.74 (10) |
C6—C1—C2 | 120.12 (13) | S2—C10—S1 | 121.74 (8) |
C3—C2—C1 | 119.57 (13) | N1—C11—C12 | 114.59 (11) |
C3—C2—H2 | 120.2 | N1—C11—H11A | 108.6 |
C1—C2—H2 | 120.2 | C12—C11—H11A | 108.6 |
C2—C3—C4 | 121.39 (13) | N1—C11—H11B | 108.6 |
C2—C3—H3 | 119.3 | C12—C11—H11B | 108.6 |
C4—C3—H3 | 119.3 | H11A—C11—H11B | 107.6 |
C3—C4—C5 | 119.69 (14) | C13—C12—C11 | 127.06 (14) |
C3—C4—H4 | 120.2 | C13—C12—H12 | 116.5 |
C5—C4—H4 | 120.2 | C11—C12—H12 | 116.5 |
C4—C5—C6 | 118.87 (12) | C12—C13—H13A | 120.0 |
C4—C5—C7 | 124.13 (12) | C12—C13—H13B | 120.0 |
C6—C5—C7 | 117.00 (11) | H13A—C13—H13B | 120.0 |
C1—C6—C5 | 120.35 (12) | O2—C14—H14A | 109.5 |
C1—C6—H6 | 119.8 | O2—C14—H14B | 109.5 |
C5—C6—H6 | 119.8 | H14A—C14—H14B | 109.5 |
C8—C7—C5 | 130.67 (12) | O2—C14—H14C | 109.5 |
C8—C7—H7 | 114.7 | H14A—C14—H14C | 109.5 |
C5—C7—H7 | 114.7 | H14B—C14—H14C | 109.5 |
C7—C8—C9 | 120.39 (11) | C10—N1—C9 | 116.48 (11) |
C7—C8—S1 | 130.08 (10) | C10—N1—C11 | 123.16 (12) |
C9—C8—S1 | 109.53 (9) | C9—N1—C11 | 120.32 (11) |
O1—C9—N1 | 123.01 (13) | C1—O2—C14 | 118.75 (12) |
O1—C9—C8 | 126.62 (13) | C8—S1—C10 | 92.87 (6) |
N1—C9—C8 | 110.37 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···S1 | 0.93 | 2.55 | 3.2497 (17) | 133 |
C13—H13A···O2i | 0.93 | 2.57 | 3.441 (2) | 157 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···S1 | 0.93 | 2.55 | 3.2497 (17) | 133 |
C13—H13A···O2i | 0.93 | 2.57 | 3.441 (2) | 157 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H13NO2S2 |
Mr | 291.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 6.9841 (14), 8.3241 (18), 13.116 (3) |
α, β, γ (°) | 89.276 (9), 75.614 (9), 72.095 (10) |
V (Å3) | 701.2 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.31 × 0.27 × 0.21 |
Data collection | |
Diffractometer | Bruker X8 APEX |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.479, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28065, 4522, 3618 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.729 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.117, 1.02 |
No. of reflections | 4522 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.26 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).
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
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Compounds containing 2-thioxothiazolidin-4-one (rhodanine) and its derivatives have been reported to exhibit a broad spectrum of biological activities, such as antidiabetic, anticancer, antitubercular, anti-HIV and antiparasitic agents (Murugan et al., 2009; Chandrappa et al., 2009; Mallikarjuna et al., 2009; Murugesan et al., 2011; Zhang et al., 2009). The unusual biological activity displayed by many rhodanine-based molecules has made them attractive synthetic targets.
The molecule of the title compound is build up from a rhodanine ring (S1/N1/C8–C10) linked to an allyl group (C11–C13) at the nitrogen atom and to a 3-methoxybenzylidene ring (C1–C6) as shown in Fig. 1. In the crystal, molecules are linked by a pair of C—H···O hydrogen bonds (Table 2), forming an inversion dimer as shown in Fig. 2.