(5E)-5-(2,4-Dichloro­benzyl­idene)-2-(piperidin-1-yl)-1,3-thia­zol-4(5H)-one

Hoong-Kun Fun; Madhukar Hemamalini; Prajwal L Lobo; D Jagadeesh Prasad; Boja Poojary

doi:10.1107/S1600536811040785

. 2011 Oct 8;67(Pt 11):o2884. doi: 10.1107/S1600536811040785

(5E)-5-(2,4-Dichlorobenzylidene)-2-(piperidin-1-yl)-1,3-thiazol-4(5H)-one

Hoong-Kun Fun ^a,^*,^‡, Madhukar Hemamalini ^a, Prajwal L Lobo ^b, D Jagadeesh Prasad ^b, Boja Poojary ^b

PMCID: PMC3247615 PMID: 22219920

Abstract

In the title compound, C₁₅H₁₄Cl₂N₂OS, the piperidine ring adopts a chair conformation. The dihedral angle between the thiazolidine ring and the dichlorobenzene ring is 9.30 (4)°; this near coplanar conformation is stabilized by the formation of an intramolecular C—H⋯S hydrogen bond, which generates an S(6) ring. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming [001] chains. Weak π–π interactions [centroid–centroid separation = 3.5460 (5) Å] consolidate the structure.

Related literature

For details and properties of the 4-thiazolidinone ring system, see: Lesyk & Zimenkovsky (2004 ▶); Lesyk et al. (2007 ▶); Havrylyuk et al. (2009 ▶); Ahn et al. (2006 ▶); Park et al. (2008 ▶); Geronikaki et al. (2008 ▶); Zimenkovsky et al. (2005 ▶). For ring puckering, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₅H₁₄Cl₂N₂OS
M _r = 341.24
Monoclinic,
a = 28.5303 (3) Å
b = 7.4915 (1) Å
c = 15.4789 (2) Å
β = 116.407 (1)°
V = 2963.17 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 100 K
0.44 × 0.25 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.783, T _max = 0.928
46944 measured reflections
6673 independent reflections
5955 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.074
S = 1.03
6673 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811040785/hb6435sup1.cif

e-67-o2884-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040785/hb6435Isup2.hkl

e-67-o2884-Isup2.hkl^{(320.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811040785/hb6435Isup3.cml

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
C1—H1A⋯S1	0.95	2.49	3.2260 (8)	134
C4—H4A⋯O1ⁱ	0.95	2.40	3.3080 (9)	160
C15—H15A⋯O1ⁱⁱ	0.99	2.57	3.2778 (11)	129

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

Acknowledgments

HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

The 4-thiazolidinone ring system is a core structure in various synthetic compounds displaying a broad spectrum of biological activities (Lesyk & Zimenkovsky, 2004), including an anticancer effect (Lesyk et al., 2007; Havrylyuk et al., 2009). The mechanisms of antitumor activity by 4-thiazolidinones and related heterocycles may be associated with their affinities to anticancer bio-targets, such as phosphatase of a regenerating liver (PRL-3) (Ahn et al., 2006; Park et al., 2008) and nonmembrane protein tyrosine phosphatase (SHP-2)(Geronikaki et al., 2008). 5-Arylidene derivatives were previously shown as the most active group of compounds with the anticancer activity among a large pool of 4-azolidone derivatives and analogs (Zimenkovsky et al., 2005). This prompted us to synthesize the title compound, (I), (Fig. 1).

The piperidine ((N2/C11–C15) ring adopts a chair conformation [Q = 0.5462 (10) Å; θ = 5.78 (10)° and φ = 206.6 (10)°; Cremer & Pople, 1975]. The central thiazolidine (S1/N1/C8–C10) ring makes dihedral angles of 21.18 (4)° and 9.30 (4)° with the terminal piperidine (N2/C11–C15) and phenyl (C1–C6) rings. The corresponding angle between the piperidine and phenyl (N2/C11–C15)/(C1–C6) rings is 13.69 (4)°. An intramolecular C1—H1A···S1 hydrogen bond generates an S(6) (Bernstein et al., 1995) ring motif.

In the crystal structure, (Fig. 2), the molecules are connected via intermolecular C—H···O (Table 1) hydrogen bonds forming one-dimensional supramolecular chains along the c-axis. The crystal structure is further stabilized by weak π–π interactions between the thiazolidine (Cg1; S1/N1/C8–C10) and phenyl (Cg3; C1–C6) rings [Cg1···Cg3 = 3.5460 (5) Å; 1/2-x, 3/2-y, 1-z].

Experimental

An equimolar mixture of 2-(4-methylsulfanylphenyl)acetohydrazide and 4-chlorobenzaldehyde was refluxed for four hours in the presence of few drops of acid catalyst and ethanol as solvent. The compound obtained was filtered, washed, dried and recrystalised from ethanol to yield brown blocks of (I).