N-[2-(4-Chloro­phen­yl)-5-methyl-4-oxo-1,3-thia­zolidin-3-yl]pyridine-3-carboxamide

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

doi:10.1107/S1600536811007136

. 2011 Mar 2;67(Pt 4):o745–o746. doi: 10.1107/S1600536811007136

N-[2-(4-Chlorophenyl)-5-methyl-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: PMC3099898 PMID: 21754043

Abstract

The title compound, C₁₆H₁₄ClN₃O₂S, crystallizes with two molecules in the asymmetric unit. In the 1,3-thiazolidine rings, the carbonyl O atoms, the S atoms, the methyl groups and the ring carbon attached to the methyl groups are disordered with occupancy ratios of 0.509 (7):0.491 (7) in one molecule and 0.464 (14):0.536 (14) in the other. The crystal structure is stabilized by intermolecular N—H⋯N, C—H⋯O hydrogen bonds and C—H⋯Cl interactions. In addition, there is a π–π stacking interaction [centroid–centroid distance = 3.794 (3) Å] between the benzene and pyridine rings.

Related literature

For the biological and pharmaceutical properties of nicotinamide derivatives, see: Barreca et al. (2003 ▶); Chen et al. (2009 ▶); Güzeldemirci et al. (2010 ▶); Gaudineau & Auclair (2004 ▶); Jaju et al. (2009 ▶); Joy et al. (2005 ▶); Karali et al. (1998 ▶); Mitchell et al. (2009 ▶); Ozkirimli et al. (2009 ▶); Patel & Shaikh (2010 ▶); Vigorita et al. (2003 ▶).

Experimental

Crystal data

C₁₆H₁₄ClN₃O₂S
M _r = 347.82
Triclinic,
a = 11.4481 (7) Å
b = 12.0276 (7) Å
c = 12.5556 (7) Å
α = 91.798 (5)°
β = 100.282 (5)°
γ = 98.068 (5)°
V = 1681.39 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 296 K
0.75 × 0.46 × 0.24 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.772, T _max = 0.918
27641 measured reflections
7719 independent reflections
3832 reflections with I > 2σ(I)
R _int = 0.079

Refinement

R[F ² > 2σ(F ²)] = 0.079
wR(F ²) = 0.225
S = 1.04
7719 reflections
472 parameters
22 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.36 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: SHELXS97 (Sheldrick, 2008 ▶); 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/S1600536811007136/qm2002sup1.cif

e-67-0o745-sup1.cif^{(44.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007136/qm2002Isup2.hkl

e-67-0o745-Isup2.hkl^{(377.6KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN2⋯N6ⁱ	0.85 (3)	2.09 (3)	2.932 (5)	168 (3)
N5—HN5⋯N3ⁱⁱ	0.86 (4)	2.16 (4)	2.950 (5)	153 (4)
C5—H5⋯O2ⁱⁱⁱ	0.93	2.42	3.245 (6)	147
C14—H14⋯O1Aⁱⁱ	0.93	2.58	3.160 (14)	121
C16—H16⋯O3Bⁱⁱ	0.93	2.50	3.242 (15)	136
C17—H17⋯O4^iv	0.93	2.50	3.367 (6)	155
C26B—H26D⋯Cl1^v	0.96	2.76	3.373 (13)	123
C31—H31⋯O3B^vi	0.93	2.45	3.139 (13)	131

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

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). This work was supported by the Scientific Research Projects Coordination Unit of Istanbul University (project No. T-3691).

supplementary crystallographic information

Comment

Nicotinamide inhibit apoptosis and necrosis by the preservation of membrane phosphatidyl- serine asymmetry (Gaudineau and Auclair, 2004). Nicotinamide derivatives are important pharmaceutical compounds.They exhibit diverse bioactivities such as antimycobacterial (Jaju et al., 2009),antimicrobial (Patel and Shaikh, 2010), CB₂ receptor agonist (Mitchell et al., 2009) properties. On the other hand 4-thiazolidinone derivatives have been shown to exhibit antifungal (Karali et al., 1998; Ozkirimli et al., 2009) reverse transcriptase inhibitor (Barreca et al., 2003), hypoglycemic (Joy et al., 2005) antimicrobial (Chen et al., 2009; Güzeldemirci et al., 2010), antiinlammatory (Vigorita et al., 2003) activities. We combine these two moieties as a part of an ongoing project directed towards the design and synthesis of antiviral molecules bearing 4-thiazolidinone and pyridine-3-carboxamide scaffolds together.

The title compound (I), (Fig. 1), crystallizes in space group P-1 with two crystallographically independent molecules per asymmetric unit. The geometries of the two molecules of (I) are very similar.

In the 1,3-thiazolidine rings of both the A and B molecules, the carboxyl oxygens, the sulfur atoms, the methyl groups and the ring carbon attached to the methyl groups are disordered with site occupancies of 0.509 (7) and 0.491 (7) for S1, molecule A, and site occupancies of 0.464 (14) and 0.536 (14) for S2, molecule B.

In the 1,3-thiazolidine groups of (I), the dihedral angles between the mean planes of two components of the disordered rings are 10.8 (5)° for molecule A and 15.2 (5)° for molecule B.

The benzene and pyridine rings make dihedral angles of 83.9 (2) and 84.88 (19)° for molecules A and B, respectively.

Intramolecular C—H···N hydrogen bonding influences the molecular conformations. The crystal structure is stabilized by the intermolecular N—H···N, C—H···O hydrogen bonds and C—H···Cl interactions. In addition, there is a π-π stacking interaction between the pyridine and benzene rings [Cg4···Cg7(1 - x, 1 - y, -z) = 3.794 (3) Å, Cg4 and Cg7 are the centroids of the C1–C6 benzene and N6/C28–C32 pyridine rings].

Experimental

0.01 mol of N'-(4-chlorobenzylidine)pyridine-3-carbohydrazide was reacted with 0.028 mol of 2-mercaptopropanoic acid in anhydrous benzene for 10 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 N-[5-methyl-2-(4-chlorophenyl)-4-oxo-1,3-thiazolidin-3-yl]pyridine-3-carboxamide. Yield: 56.48%; m.p.: 443.1–447.4 K. UV (EtOH) λ max: 202.8, 220.6, 257.2 nm. IR (KBr) υ: 1673 (amide C=O), 1728 (thia C=O) cm^-1; ¹H-NMR (DMSO-d₆, 500 MHz): 1.55 (3H, d, J=7.0 Hz, CH₃-thia.), 4.13 (1H, q, J= 7.0 Hz, H5-thia.), 4.23 (1H, dq, J=6.8, 1.47 Hz, H5-thia.), 5.92 (1H, s, H2-thia), 7.43–7.47 (2H, m, 2-C₆H₄-(H2,6)-thia.), 7.48–7.50 (1H, m, H5-pyridine), 7.52–7.53 (2H, m, 2-C₆H₄-(H3,5)-thia.), 8.04–8.09 (1H, m, H4-pyridine), 8.73 (1H, dd, J₌6.3 Hz, 1.4 Hz, H6-pyridine), 8.84, 8.85 (1H, 2 d, J=2.9, 1.4 Hz, H2-pyridine), 10.94 (1H, s, CONH) p.p.m.; ESI– (m/z, relative abundance): 347.68 ([M—H+2]^-, 25.16), 345.56 ([M—H]^-, 100). Analysis calculated for C₁₆H₁₄ClN₃O₂S. 0.5 EtOH: C 55.06, H 4.62, N 11.48%. Found: C 55.19, H 5.15, N 12.02%.