3-(2-Methyl­phen­yl)-2-thioxo-1,3-thia­zolidin-4-one

Shahwar, D.; Tahir, M.N.; Yasmeen, A.; Ahmad, N.; Khan, M.A.

doi:10.1107/S1600536809045814

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3014

doi:10.1107/S1600536809045814

Open

access

3-(2-Methylphenyl)-2-thioxo-1,3-thiazolidin-4-one

Durre Shahwar,^a M. Nawaz Tahir,^b ^* Asma Yasmeen,^a Naeem Ahmad ^a and Muhammad Akmal Khan ^a

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 31 October 2009; accepted 1 November 2009; online 7 November 2009)

In the title compound, C₁₀H₉NOS₂, the 1,3-thiazolidine and 2-methylphenyl rings are oriented at a dihedral angle of 84.44 (9)°. In the crystal, an unusual bifurcated C—H⋯(O,π) interaction leads to zigzag chains of molecules.

Related literature

For background to rhodanine derivatives, see: Cutshall et al. (2005 ). For related structures, see: Shahwar et al. (2009a ,b ,c ).

Experimental

Crystal data

C₁₀H₉NOS₂
M_r = 223.30
Monoclinic, C 2/c
a = 23.690 (5) Å
b = 7.1401 (17) Å
c = 14.628 (3) Å
β = 122.215 (6)°
V = 2093.5 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 296 K
0.34 × 0.16 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.914, T_max = 0.934
10878 measured reflections
2661 independent reflections
1436 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.189
S = 1.02
2661 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.97	2.58	3.214 (5)	123
C8—H8A⋯Cg2ⁱ	0.97	2.65	3.420 (4)	137
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg2 is the centroid of the C1–C6 ring.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045814/hb5205sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045814/hb5205Isup2.hkl

checkCIF report

Comment top

Rhodanine-based molecules have been popular as small molecule inhibitors of numerous targets such as HCV NS3 protease, aldose reductase, beta-lactamase, UDP-N-acetylmuramate/L-alanine ligase, antidiabetic agents, cathepsin D, and histidine decarboxylase (Cutshall et al., 2005). We herein, report the crystal structure and preparation of the title compound (I, Fig. 1) which is one of the rhodanine derivatives from the series of compounds prepared by our group for beta-lactamase and xanthine oxidase enzyme inhibition studies.

The crystal structures of (II) (5Z)-5-(2-Hydroxybenzylidene)-3-phenyl- 2-thioxo-1,3-thiazolidin-4-one (Shahwar et al., 2009a), (III) (5E)-5-(4-Hydroxy-3-methoxybenzylidene)-2-thioxo-1, 3-thiazolidin-4-one methanol monosolvate (Shahwar et al., 2009b) and (IV) (5Z)-5-(2-Hydroxybenzylidene)-2-thioxo-1,3-thiazolidin-4-one methanol hemisolvate (Shahwar et al., 2009c) have been reported which are the rhodanine derivatives. The crystal stucture of (II) contains (I) as a group.

In (I), the 2-methylphenyl A (C1–C6/C10) and the rhodanine group B (N1/C7/C8/S1/C9/O1/S2) are planar with maximum r. m. s. deviations of 0.0051 and 0.0387 Å respectively, from their mean square planes. The dihedral angle between A/B is 84.44 (9)°. The molecules are stabilized in the form of zig–zag infinte one dimensional polymeric chains due to intermolecular H-bondings (Table 1, Fig. 2). The C–H···π interaction (Table 1) also play a role in stabilizing the molecules.

Related literature top

For background to rhodanine derivatives, see: Cutshall et al. (2005). For related structures, see: Shahwar et al. (2009a,b,c). Cg2 is the centroid of the C1–C6 ring.

Experimental top

The title compound was prepared by a three step reaction procedure. In the first step ortho toluidine aniline (10.7 g, 0.1 mol) and triethylamine (50.5 g, 0.5 mol) were stirred in ethanol (20 ml) followed by dropwise addition of CS₂ (15.2 g, 0.2 mol) while keeping the flask in an ice bath. The precipitate obtained were filtered off and washed with diethyl ether.

In second step, a solution of sodium chloroacetate (11.6 g, 0.1 mol) and chloroacetic acid (18.9 g, 0.2 mol) was prepared in 50 ml distilled water. To this solution the precipitates obtained in first step were added gradually and stirred at 273 K. This mixture was stirred untill it turned dark yellow.

In third step the yellow mixture was mixed in 140 ml hot (363–368 K) hydrochloric acid (6 N) and stirred for five minutes to obtain colorless crystalline precipitates. These precipitates were recrystalized in chloroform to get the dark yellow needles of (I).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.

3-(2-Methylphenyl)-2-thioxo-1,3-thiazolidin-4-one top

Crystal data top

C₁₀H₉NOS₂	F(000) = 928
M_r = 223.30	D_x = 1.417 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2661 reflections
a = 23.690 (5) Å	θ = 2.8–28.7°
b = 7.1401 (17) Å	µ = 0.47 mm⁻¹
c = 14.628 (3) Å	T = 296 K
β = 122.215 (6)°	Cut needle, dark yellow
V = 2093.5 (8) Å³	0.34 × 0.16 × 0.14 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	2661 independent reflections
Radiation source: fine-focus sealed tube	1436 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.7°, θ_min = 2.8°
ω scans	h = −31→30
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→5
T_min = 0.914, T_max = 0.934	l = −17→19
10878 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.189	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0949P)² + 0.6816P] where P = (F_o² + 2F_c²)/3
2661 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₀H₉NOS₂	V = 2093.5 (8) Å³
M_r = 223.30	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.690 (5) Å	µ = 0.47 mm⁻¹
b = 7.1401 (17) Å	T = 296 K
c = 14.628 (3) Å	0.34 × 0.16 × 0.14 mm
β = 122.215 (6)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2661 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1436 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.934	R_int = 0.061
10878 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.189	H-atom parameters constrained
S = 1.02	Δρ_max = 0.63 e Å⁻³
2661 reflections	Δρ_min = −0.31 e Å⁻³
128 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.21396 (5)	−0.00494 (13)	−0.00417 (7)	0.0612 (3)
S2	0.07182 (5)	0.09169 (18)	−0.10373 (8)	0.0903 (4)
O1	0.26644 (11)	0.2834 (4)	0.24779 (19)	0.0733 (9)
N1	0.17183 (11)	0.1968 (3)	0.09176 (18)	0.0475 (8)
C1	0.12842 (14)	0.2941 (4)	0.1167 (2)	0.0499 (10)
C2	0.11018 (15)	0.4752 (5)	0.0824 (2)	0.0527 (10)
C3	0.06977 (17)	0.5655 (6)	0.1131 (3)	0.0672 (12)
C4	0.05067 (19)	0.4719 (7)	0.1737 (3)	0.0768 (16)
C5	0.0691 (2)	0.2946 (7)	0.2068 (3)	0.0779 (16)
C6	0.10811 (17)	0.2011 (6)	0.1777 (3)	0.0660 (14)
C7	0.23984 (15)	0.1956 (5)	0.1655 (2)	0.0509 (11)
C8	0.27516 (16)	0.0721 (5)	0.1295 (3)	0.0555 (11)
C9	0.14858 (16)	0.1022 (4)	−0.0033 (3)	0.0537 (11)
C10	0.1303 (2)	0.5694 (6)	0.0175 (3)	0.0726 (14)
H3	0.05615	0.68853	0.09201	0.0808*
H4	0.02385	0.53341	0.19283	0.0918*
H5	0.05568	0.23555	0.24881	0.0933*
H6	0.12066	0.07745	0.19869	0.0793*
H8A	0.29480	−0.03430	0.17767	0.0668*
H8B	0.31039	0.14084	0.12918	0.0668*
H10A	0.11483	0.50009	−0.04790	0.1090*
H10B	0.17806	0.57808	0.05699	0.1090*
H10C	0.11140	0.69291	0.00017	0.1090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0782 (6)	0.0598 (6)	0.0604 (5)	0.0158 (4)	0.0468 (5)	0.0023 (4)
S2	0.0723 (7)	0.0974 (9)	0.0678 (7)	0.0173 (6)	0.0150 (5)	−0.0333 (6)
O1	0.0542 (14)	0.097 (2)	0.0562 (14)	0.0095 (13)	0.0211 (12)	−0.0126 (14)
N1	0.0499 (14)	0.0541 (16)	0.0422 (13)	0.0081 (11)	0.0271 (12)	−0.0011 (11)
C1	0.0464 (16)	0.0565 (19)	0.0440 (16)	0.0030 (13)	0.0222 (14)	−0.0077 (14)
C2	0.0533 (18)	0.064 (2)	0.0423 (16)	0.0056 (14)	0.0265 (15)	−0.0023 (14)
C3	0.060 (2)	0.075 (2)	0.057 (2)	0.0178 (17)	0.0247 (17)	−0.0056 (18)
C4	0.057 (2)	0.121 (4)	0.061 (2)	0.002 (2)	0.0373 (19)	−0.013 (2)
C5	0.076 (3)	0.103 (3)	0.074 (2)	−0.016 (2)	0.053 (2)	−0.012 (2)
C6	0.066 (2)	0.086 (3)	0.0577 (19)	−0.0094 (18)	0.0409 (18)	−0.0094 (18)
C7	0.0538 (18)	0.059 (2)	0.0442 (17)	0.0084 (15)	0.0291 (15)	0.0084 (15)
C8	0.0607 (19)	0.063 (2)	0.0565 (18)	0.0147 (15)	0.0404 (17)	0.0164 (16)
C9	0.069 (2)	0.0464 (18)	0.0475 (17)	0.0080 (14)	0.0323 (16)	−0.0041 (14)
C10	0.089 (3)	0.062 (2)	0.079 (2)	0.0073 (19)	0.053 (2)	0.008 (2)

Geometric parameters (Å, º) top

S1—C8	1.790 (4)	C4—C5	1.343 (7)
S1—C9	1.734 (4)	C5—C6	1.379 (7)
S2—C9	1.619 (4)	C7—C8	1.492 (6)
O1—C7	1.196 (4)	C3—H3	0.9300
N1—C1	1.440 (4)	C4—H4	0.9300
N1—C7	1.381 (4)	C5—H5	0.9300
N1—C9	1.370 (4)	C6—H6	0.9300
C1—C2	1.371 (5)	C8—H8A	0.9700
C1—C6	1.388 (5)	C8—H8B	0.9700
C2—C3	1.412 (6)	C10—H10A	0.9600
C2—C10	1.436 (6)	C10—H10B	0.9600
C3—C4	1.366 (6)	C10—H10C	0.9600

C8—S1—C9	93.61 (19)	S2—C9—N1	126.4 (3)
C1—N1—C7	119.9 (2)	C2—C3—H3	120.00
C1—N1—C9	122.7 (3)	C4—C3—H3	120.00
C7—N1—C9	117.4 (3)	C3—C4—H4	119.00
N1—C1—C2	119.4 (3)	C5—C4—H4	119.00
N1—C1—C6	118.1 (3)	C4—C5—H5	120.00
C2—C1—C6	122.5 (3)	C6—C5—H5	120.00
C1—C2—C3	116.7 (3)	C1—C6—H6	120.00
C1—C2—C10	122.2 (4)	C5—C6—H6	120.00
C3—C2—C10	121.1 (4)	S1—C8—H8A	110.00
C2—C3—C4	119.9 (4)	S1—C8—H8B	110.00
C3—C4—C5	122.6 (5)	C7—C8—H8A	110.00
C4—C5—C6	119.2 (4)	C7—C8—H8B	110.00
C1—C6—C5	119.1 (4)	H8A—C8—H8B	109.00
O1—C7—N1	123.5 (3)	C2—C10—H10A	109.00
O1—C7—C8	124.9 (3)	C2—C10—H10B	109.00
N1—C7—C8	111.6 (3)	C2—C10—H10C	109.00
S1—C8—C7	106.7 (3)	H10A—C10—H10B	110.00
S1—C9—S2	123.3 (2)	H10A—C10—H10C	110.00
S1—C9—N1	110.4 (3)	H10B—C10—H10C	110.00

C9—S1—C8—C7	−4.5 (3)	C7—N1—C9—S2	−177.0 (3)
C8—S1—C9—S2	−179.4 (2)	N1—C1—C2—C3	−177.5 (3)
C8—S1—C9—N1	1.8 (3)	N1—C1—C2—C10	3.1 (4)
C7—N1—C1—C2	94.3 (3)	C6—C1—C2—C3	0.6 (5)
C7—N1—C1—C6	−84.0 (4)	C6—C1—C2—C10	−178.8 (3)
C9—N1—C1—C2	−86.2 (4)	N1—C1—C6—C5	177.0 (3)
C9—N1—C1—C6	95.6 (4)	C2—C1—C6—C5	−1.2 (5)
C1—N1—C7—O1	−5.7 (5)	C1—C2—C3—C4	−0.2 (5)
C1—N1—C7—C8	174.3 (3)	C10—C2—C3—C4	179.2 (4)
C9—N1—C7—O1	174.7 (3)	C2—C3—C4—C5	0.4 (6)
C9—N1—C7—C8	−5.4 (4)	C3—C4—C5—C6	−0.9 (7)
C1—N1—C9—S1	−177.9 (2)	C4—C5—C6—C1	1.3 (6)
C1—N1—C9—S2	3.4 (4)	O1—C7—C8—S1	−173.9 (3)
C7—N1—C9—S1	1.8 (3)	N1—C7—C8—S1	6.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.97	2.58	3.214 (5)	123
C8—H8A···Cg2ⁱ	0.97	2.65	3.420 (4)	137

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₉NOS₂
M_r	223.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	23.690 (5), 7.1401 (17), 14.628 (3)
β (°)	122.215 (6)
V (Å³)	2093.5 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.34 × 0.16 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.914, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	10878, 2661, 1436
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.189, 1.02
No. of reflections	2661
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.31

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.97	2.58	3.214 (5)	123
C8—H8A···Cg2ⁱ	0.97	2.65	3.420 (4)	137

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

Durre Shahwar is grateful to Government College University, Lahore, for providing funds under the GCU funded Research Projects Programme.

References

Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cutshall, N. S., O'Day, C. & Prezhdo, M. (2005). Bioorg. Med. Chem. Lett. 15, 3374–3379. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Shahwar, D., Tahir, M. N., Raza, M. A. & Iqbal, B. (2009a). Acta Cryst. E65, o2903. Web of Science CrossRef IUCr Journals Google Scholar
Shahwar, D., Tahir, M. N., Raza, M. A., Iqbal, B. & Naz, S. (2009b). Acta Cryst. E65, o2637. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shahwar, D., Tahir, M. N., Raza, M. A., Saddaf, M. & Majeed, S. (2009c). Acta Cryst. E65, o2638. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar