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

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

doi:10.1107/S1600536809045863

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3016

doi:10.1107/S1600536809045863

Open

access

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

Durre Shahwar,^a M. Nawaz Tahir,^b,^a ^* 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 1 November 2009; accepted 1 November 2009; online 7 November 2009)

In the title compound, C₁₀H₉NOS₂, the dihedral angle between the rhodanine (2-thioxo-1,3-thiazolidin-4-one) and 3-methylphenyl rings is 83.30 (3)°. The H atoms of the methyl group are disordered over two set of sites with an occupancy ratio of 0.58 (3):0.42 (3). In the crystal, the molecules interact by way of C—H⋯π and C=O⋯π interactions.

Related literature

For related structures, see: Shahwar et al. (2009a ,b ,c ,d ,e ).

Experimental

Crystal data

C₁₀H₉NOS₂
M_r = 223.3
Monoclinic, P 2₁ /c
a = 8.0775 (3) Å
b = 6.4058 (2) Å
c = 21.4715 (7) Å
β = 106.068 (2)°
V = 1067.59 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 296 K
0.32 × 0.24 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.849, T_max = 0.897
11841 measured reflections
2666 independent reflections
2116 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.087
S = 1.03
2666 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cg2ⁱ	0.97	2.59	3.5219 (17)	162
C7—O1⋯Cg1ⁱ	1.20 (1)	2.94 (1)	4.1070 (16)	164 (1)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 and Cg2 are the centroids of the S1/C8/C7/N1/C9 and C1—C6 rings, respectively.

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 for Windows (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/S1600536809045863/hb5208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045863/hb5208Isup2.hkl

checkCIF report

Comment top

We have reported the synthesis and crystal structures of various rhodanine derivatives such as (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), (IV) (5Z)-5-(2-Hydroxybenzylidene)-2-thioxo-1,3-thiazolidin-4-one methanol hemisolvate (Shahwar et al., 2009c), (V) 3-(2-Methylphenyl)-2-thioxo-1,3-thiazolidin-4-one (Shahwar et al., 2009d) and (VI) 3-Cyclohexyl-2-thioxo-1,3-thiazolidin-4-one (Shahwar et al., 2009e). The purpose of synthesis of differet rhodanine derivatives is to study the biological activities. The title compound (I, Fig. 1) is being reported in this context.

In (I), the 3-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 0.0068 and 0.0171 Å respectively, from their mean square planes. The dihedral angle between A/B is 83.30 (3)°. The H-atoms of the methyl moiety are disordered over two set of sites with occupancy ratio of 0.58 (3):0.42 (3) in the monomers. There exist C–H···π and C==O···π interactions (Table 1) which stabilize the molecules.

Related literature top

For related structures, see: Shahwar et al. (2009a,b,c,d,e). Cg1 and Cg2 are the centroids of the S1/C8/C7/N1/C9 and C1—C6 rings, respectively.

Experimental top

The title compound was prepared by a three step reaction procedure. In the first step meta 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 light 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 light yellow prisms 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 for Windows (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-(3-Methylphenyl)-2-thioxo-1,3-thiazolidin-4-one top

Crystal data top

C₁₀H₉NOS₂	F(000) = 464
M_r = 223.3	D_x = 1.389 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2666 reflections
a = 8.0775 (3) Å	θ = 2.6–28.3°
b = 6.4058 (2) Å	µ = 0.46 mm⁻¹
c = 21.4715 (7) Å	T = 296 K
β = 106.068 (2)°	Prism, light yellow
V = 1067.59 (6) Å³	0.32 × 0.24 × 0.22 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2666 independent reflections
Radiation source: fine-focus sealed tube	2116 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 2.6°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −8→8
T_min = 0.849, T_max = 0.897	l = −28→28
11841 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0399P)² + 0.2635P] where P = (F_o² + 2F_c²)/3
2666 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₉NOS₂	V = 1067.59 (6) Å³
M_r = 223.3	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0775 (3) Å	µ = 0.46 mm⁻¹
b = 6.4058 (2) Å	T = 296 K
c = 21.4715 (7) Å	0.32 × 0.24 × 0.22 mm
β = 106.068 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2666 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2116 reflections with I > 2σ(I)
T_min = 0.849, T_max = 0.897	R_int = 0.026
11841 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.03	Δρ_max = 0.27 e Å⁻³
2666 reflections	Δρ_min = −0.22 e Å⁻³
129 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	Occ. (<1)
S1	0.90452 (5)	0.42703 (7)	0.26996 (2)	0.0484 (1)
S2	0.85641 (6)	0.38555 (7)	0.12935 (2)	0.0511 (2)
O1	0.54228 (16)	0.04248 (19)	0.26950 (6)	0.0537 (4)
N1	0.67528 (14)	0.18699 (18)	0.19889 (5)	0.0324 (3)
C1	0.56186 (18)	0.0913 (2)	0.14230 (7)	0.0337 (4)
C2	0.5937 (2)	−0.1103 (2)	0.12588 (8)	0.0419 (5)
C3	0.4818 (2)	−0.1972 (3)	0.07148 (8)	0.0501 (6)
C4	0.3436 (2)	−0.0858 (3)	0.03533 (8)	0.0518 (6)
C5	0.3103 (2)	0.1156 (3)	0.05186 (7)	0.0461 (5)
C6	0.42217 (18)	0.2036 (3)	0.10687 (7)	0.0391 (5)
C7	0.65129 (19)	0.1553 (2)	0.26005 (7)	0.0363 (4)
C8	0.77847 (19)	0.2774 (3)	0.31088 (7)	0.0410 (5)
C9	0.80207 (17)	0.3243 (2)	0.19488 (7)	0.0342 (4)
C10	0.1604 (2)	0.2403 (4)	0.01220 (10)	0.0730 (8)
H2	0.68758	−0.18517	0.15069	0.0502*
H3	0.50036	−0.33254	0.05925	0.0602*
H4	0.27025	−0.14709	−0.00126	0.0621*
H6	0.40257	0.33792	0.11964	0.0469*
H8A	0.85188	0.18403	0.34219	0.0492*
H8B	0.71912	0.36922	0.33352	0.0492*
H10A	0.06610	0.23026	0.03116	0.1095*	0.58 (3)
H10B	0.12550	0.18649	−0.03121	0.1095*	0.58 (3)
H10C	0.19388	0.38382	0.01132	0.1095*	0.58 (3)
H10D	0.19424	0.31376	−0.02127	0.1095*	0.42 (3)
H10E	0.12470	0.33875	0.03963	0.1095*	0.42 (3)
H10F	0.06653	0.14807	−0.00708	0.1095*	0.42 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0426 (2)	0.0565 (3)	0.0445 (2)	−0.0166 (2)	0.0092 (2)	−0.0128 (2)
S2	0.0545 (3)	0.0578 (3)	0.0449 (2)	−0.0180 (2)	0.0202 (2)	−0.0016 (2)
O1	0.0636 (8)	0.0544 (7)	0.0476 (7)	−0.0196 (6)	0.0227 (6)	0.0006 (5)
N1	0.0328 (6)	0.0310 (5)	0.0331 (6)	−0.0024 (5)	0.0088 (5)	−0.0023 (5)
C1	0.0341 (7)	0.0342 (7)	0.0343 (7)	−0.0077 (6)	0.0120 (6)	−0.0027 (6)
C2	0.0433 (8)	0.0364 (8)	0.0482 (9)	−0.0029 (6)	0.0166 (7)	−0.0041 (7)
C3	0.0592 (10)	0.0442 (9)	0.0529 (10)	−0.0167 (8)	0.0253 (8)	−0.0169 (8)
C4	0.0521 (10)	0.0673 (11)	0.0375 (8)	−0.0261 (9)	0.0150 (7)	−0.0131 (8)
C5	0.0379 (8)	0.0627 (10)	0.0371 (8)	−0.0096 (7)	0.0094 (6)	0.0066 (7)
C6	0.0385 (8)	0.0399 (8)	0.0395 (8)	−0.0039 (6)	0.0119 (6)	0.0011 (6)
C7	0.0395 (8)	0.0343 (7)	0.0359 (7)	0.0028 (6)	0.0118 (6)	0.0018 (6)
C8	0.0388 (8)	0.0481 (9)	0.0351 (7)	0.0015 (7)	0.0087 (6)	−0.0026 (7)
C9	0.0314 (7)	0.0319 (7)	0.0389 (7)	−0.0006 (5)	0.0091 (6)	−0.0025 (6)
C10	0.0505 (11)	0.0965 (17)	0.0611 (12)	−0.0013 (11)	−0.0027 (9)	0.0161 (11)

Geometric parameters (Å, º) top

S1—C8	1.7952 (17)	C7—C8	1.496 (2)
S1—C9	1.7258 (15)	C2—H2	0.9300
S2—C9	1.6335 (15)	C3—H3	0.9300
O1—C7	1.199 (2)	C4—H4	0.9300
N1—C1	1.4406 (18)	C6—H6	0.9300
N1—C7	1.3943 (18)	C8—H8A	0.9700
N1—C9	1.3707 (18)	C8—H8B	0.9700
C1—C2	1.3814 (19)	C10—H10A	0.9600
C1—C6	1.376 (2)	C10—H10B	0.9600
C2—C3	1.381 (2)	C10—H10C	0.9600
C3—C4	1.371 (2)	C10—H10D	0.9600
C4—C5	1.384 (3)	C10—H10E	0.9600
C5—C6	1.392 (2)	C10—H10F	0.9600
C5—C10	1.503 (3)

C8—S1—C9	93.63 (7)	C2—C3—H3	120.00
C1—N1—C7	120.71 (12)	C4—C3—H3	120.00
C1—N1—C9	122.13 (11)	C3—C4—H4	119.00
C7—N1—C9	116.98 (11)	C5—C4—H4	119.00
N1—C1—C2	119.55 (13)	C1—C6—H6	120.00
N1—C1—C6	118.46 (13)	C5—C6—H6	120.00
C2—C1—C6	121.98 (14)	S1—C8—H8A	110.00
C1—C2—C3	117.92 (15)	S1—C8—H8B	110.00
C2—C3—C4	120.60 (17)	C7—C8—H8A	110.00
C3—C4—C5	121.72 (16)	C7—C8—H8B	110.00
C4—C5—C6	117.93 (16)	H8A—C8—H8B	109.00
C4—C5—C10	122.24 (16)	C5—C10—H10A	109.00
C6—C5—C10	119.83 (17)	C5—C10—H10B	109.00
C1—C6—C5	119.84 (16)	C5—C10—H10C	109.00
O1—C7—N1	123.17 (14)	C5—C10—H10D	109.00
O1—C7—C8	125.44 (14)	C5—C10—H10E	109.00
N1—C7—C8	111.39 (12)	C5—C10—H10F	109.00
S1—C8—C7	106.86 (10)	H10A—C10—H10B	109.00
S1—C9—S2	122.64 (8)	H10A—C10—H10C	109.00
S1—C9—N1	111.07 (10)	H10B—C10—H10C	109.00
S2—C9—N1	126.29 (11)	H10D—C10—H10E	109.00
C1—C2—H2	121.00	H10D—C10—H10F	109.00
C3—C2—H2	121.00	H10E—C10—H10F	109.00

C9—S1—C8—C7	−2.42 (12)	C7—N1—C9—S2	179.24 (11)
C8—S1—C9—S2	−177.72 (10)	N1—C1—C2—C3	179.72 (14)
C8—S1—C9—N1	1.42 (11)	C6—C1—C2—C3	1.1 (2)
C7—N1—C1—C2	−85.14 (18)	N1—C1—C6—C5	179.89 (14)
C7—N1—C1—C6	93.56 (16)	C2—C1—C6—C5	−1.5 (2)
C9—N1—C1—C2	99.88 (17)	C1—C2—C3—C4	−0.2 (2)
C9—N1—C1—C6	−81.42 (18)	C2—C3—C4—C5	−0.4 (3)
C1—N1—C7—O1	3.2 (2)	C3—C4—C5—C6	0.0 (3)
C1—N1—C7—C8	−177.29 (12)	C3—C4—C5—C10	179.27 (17)
C9—N1—C7—O1	178.41 (14)	C4—C5—C6—C1	0.9 (2)
C9—N1—C7—C8	−2.06 (18)	C10—C5—C6—C1	−178.41 (15)
C1—N1—C9—S1	175.30 (10)	O1—C7—C8—S1	−177.61 (13)
C1—N1—C9—S2	−5.60 (19)	N1—C7—C8—S1	2.88 (16)
C7—N1—C9—S1	0.14 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cg2ⁱ	0.97	2.59	3.5219 (17)	162
C7—O1···Cg1ⁱ	1.20 (1)	2.94 (1)	4.1070 (16)	164 (1)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉NOS₂
M_r	223.3
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.0775 (3), 6.4058 (2), 21.4715 (7)
β (°)	106.068 (2)
V (Å³)	1067.59 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.32 × 0.24 × 0.22

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.849, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	11841, 2666, 2116
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.087, 1.03
No. of reflections	2666
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.22

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (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—H8B···Cg2ⁱ	0.97	2.59	3.5219 (17)	162
C7—O1···Cg1ⁱ	1.199 (2)	2.9413 (14)	4.1070 (16)	163.94 (11)

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

Acknowledgements

DS 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
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
Shahwar, D., Tahir, M. N., Yasmeen, A., Ahmad, N. & Khan, M. A. (2009d). Acta Cryst. E65, o3014. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shahwar, D., Tahir, M. N., Yasmeen, A., Ahmad, N. & Khan, M. A. (2009e). Acta Cryst. E65, o3015. 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