N-[(2S)-2-(4-Bromo­phen­yl)-4-oxo-1,3-thia­zolidin-3-yl]pyridine-3-carboxamide

Mehmet Akkurt; Ísmail Çelik; Hale Demir; Sumru Özkırımlı; Orhan Büyükgüngör

doi:10.1107/S1600536810022506

. 2010 Jun 18;66(Pt 7):o1691–o1692. doi: 10.1107/S1600536810022506

N-[(2S)-2-(4-Bromophenyl)-4-oxo-1,3-thiazolidin-3-yl]pyridine-3-carboxamide

Mehmet Akkurt ^a,^*, Ísmail Çelik ^b, Hale Demir ^c, Sumru Özkırımlı ^c, Orhan Büyükgüngör ^d

PMCID: PMC3006680 PMID: 21587914

Abstract

In the title compound, C₁₅H₁₂BrN₃O₂S, the dihedral angle between the pyridine and benzene rings is 73.17 (19)°. The five-membered 1,3-thiazolidine ring has an envelope conformation, with the S atom displaced by 0.196 (1) Å from the mean plane of the four other ring atoms. An intramolecular C—H⋯N interaction occurs. The crystal structure is stabilized by intermolecular N—H⋯O and C—H⋯O hydrogen bonds and C—H⋯π interactions. In addition, a weak π–π stacking interaction is also observed between the 1,3-thiazolidine and pyridine rings [centroid–centroid distance = 3.805 (2) Å].

Related literature

For the cytoprotective and antiviral properties of nicotinamide, see: Gaudineau & Auclair (2004 ▶); Moell et al. (2009 ▶). For 3-pyridinecarboxamide derivatives with antitumor activity, see: Elbaum et al. (2003 ▶). For the various biological activities of thiazolidinones, see: Capan et al. (1999 ▶) and Ozkırımlı et al. (2009 ▶) (antifungal); Guzel et al. (2006 ▶) (antituberculosis); Rawal et al. (2007 ▶) (RT Inhibitor); Vanderlinden et al. (2010 ▶) (antiviral). For standard bond-length data, see: Allen et al. (1987 ▶). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₅H₁₂BrN₃O₂S
M _r = 378.25
Trigonal,
a = 24.9588 (9) Å
c = 12.8013 (5) Å
V = 6906.1 (4) Å³
Z = 18
Mo Kα radiation
μ = 2.82 mm⁻¹
T = 296 K
0.28 × 0.23 × 0.19 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.505, T _max = 0.616
13554 measured reflections
3174 independent reflections
1963 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.085
S = 0.95
3174 reflections
202 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022506/lh5067sup1.cif

e-66-o1691-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810022506/lh5067Isup2.hkl

e-66-o1691-Isup2.hkl^{(156.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg3 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.85 (3)	2.07 (3)	2.914 (4)	172 (4)
C3—H3⋯O2ⁱ	0.93	2.43	3.237 (5)	146
C15—H15⋯N2	0.93	2.54	2.864 (5)	101
C15—H15⋯O1ⁱ	0.93	2.50	3.399 (5)	162
C14—H14⋯Cg3ⁱⁱ	0.93	2.79	3.692 (4)	164

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund). HD and SO acknowledge the Scientific Research Projects Coordination Unit of Istanbul University (Project number T-3691).

supplementary crystallographic information

Comment

Development of new active compounds for viral infections is a high priority goal. The rapid onset of resistance and hypersensitivity reactions limit the use of antiviral compounds and therefore, there is an ongoing need for novel antiviral agents. A number of diverse chemical structures have been shown to be potent RT Inhibitors. Nicotinamide is gaining attention for its cytoprotective and antiviral properties (Gaudineau et al., 2004). Antiviral effect of nicotinamide and its inhibitory effect on enterovirus induced chemokine secretion have been recently shown (Moell et al., 2009). Furthermore, 3-pyridinecarboxamide derivatives with antitumor activity have been reported (Elbaum et al., 2003). Thiazolidinones exhibit various biological activities such as antifungal (Capan et al., 1999; Ozkırımlı et al., 2009); antituberculosis (Guzel et al., 2006); RT Inhibitor (Rawal et al., 2007); antiviral (Vanderlinden et al., 2010). We combine these two moities as part of an ongoing project directed towards the design and synthesis of bioactive molecules bearing 4-thiazolidinone and pyridine-3-carboxamide scaffolds together.

In the title molecule (I) shown in Fig. 1, the bond lengths and the bond angles are in the normal ranges (Allen et al., 1987). The C2—C1—C7—N1, C2—C1—C7—S1, N1—N2—C10—O2 and N1—N2—C10—C11 torsion angles are 40.2 (4), -76.2 (3), -0.7 (5) and -179.7 (3) °, respectively. The dihedral angle between the pyridine (N3/C11–C15) and benzene (C1–C6) rings is 73.17 (19) °. The five-membered 1,3-thiazolidine ring has an envelope conformation, with atom S1 displaced by -0.196 (1) Å from the S1/N1/C7–C9 plane [the puckering parameters (Cremer & Pople, 1975) are Q₂ = 0.361 (3) Å and φ₂ = 188.0 (5) °].

The crystal structure is stabilized by intermolecular N—H···O and C—H···O hydrogen bonding interactions (Table 1, Fig. 2) and a C—H···π interactions (Table 1). A weak π-π stacking interaction is observed between the 1,3-thiazolidine and pyridine rings [Cg2···Cg2(2/3 - x, 7/3 - y, 1/3 - z) = 3.805 (2) Å, where Cg1 and Cg2 are the centroids of the S1/N1/C7–C9 1,3-thiazolidine and N3/C11–C15 pyridine rings, respectively].

Experimental

0.01 mol of N'-(4-bromobenzylidine)pyridine-3-carbohydrazide was reacted with 0.03 mol of mercaptoacetic acid in anhydrous benzene for 8 h using a Dean-Stark trap. Excess benzene was removed under reduced pressure. The residue was triturated with saturated sodium bicarbonate solution. The separated solid was filtered, washed with water and crystallized from methanol. White crystalline solid. Yield: 60.84%; m.p.: 446.1–450.0 K. UV (EtOH) max: 202.6, 221.2, 264.8 nm. IR (KBr) υ: 1666 (amide C=O), 1687 (thia C=O); ¹H-NMR (DMSO-d₆, 400 MHz): 3.80 (1H, d, J=16 Hz, H5-thia.), 3.95 (1H, dd, J=15.8, 2.8 Hz, H5-thia.), 5.92 (1H, s, H2-thia.), 7.46 (2H, d, J=8.4 Hz, 2-C₆H₄-(H2,6)-thia.), 7.47–7.49 (1H, m, H5-pyridine), 7.56 (1H, d, J=8.8 Hz, 2-C₆H₄-(H3,5)-thia.), 8.08 (1H, dt, J=8.4, 1.6, 1.6 Hz, H4-pyridine), 8.71 (1H, dd, J=4.6, 1.6 Hz, H6-pyridine), 8.87 (1H, d, J=1.6 Hz, H2-pyridine), 10.93 (1H, s, CONH); ESI+ (m/z): 380.23 ([MH+2]⁺, 100), 378.24([MH]⁺, 98.71). Analysis calculated for C₁₅H₁₂BrN₃O₂S: C 47.63, H 3.20, N 11.11%. Found: C 47.39, H 3.09, N 10.98%.