3-Cyclo­hexyl-2-thioxo-1,3-thia­zolidin-4-one

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

doi:10.1107/S1600536809045851

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3015

doi:10.1107/S1600536809045851

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3-Cyclohexyl-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 1 November 2009; accepted 1 November 2009; online 7 November 2009)

In the title compound, C₉H₁₃NOS₂, the complete molecule is generated by crystallographic mirror symmetry, with all the non-H atoms of the rhodanine (2-thioxo-1,3-thiazolidin-4-one) system and two C atoms of the cyclohexyl ring lying on the reflecting plane. The conformation is stabilized by intramolecular C—H⋯O and C—H⋯S interactions. In the crystal, weak π–π interactions at a distance of 3.8140 (5) Å between the centroids of the heterocyclic rings occur.

Related literature

For related structures, see: Shahwar et al. (2009a ,b ,c ,d ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₃NOS₂
M_r = 215.32
Monoclinic, P 2₁ /m
a = 7.3897 (3) Å
b = 7.0999 (4) Å
c = 10.3399 (5) Å
β = 107.535 (2)°
V = 517.29 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 296 K
0.36 × 0.25 × 0.23 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.849, T_max = 0.897
5969 measured reflections
1390 independent reflections
1194 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.096
S = 1.07
1390 reflections
76 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯S2	0.98	2.61	3.158 (2)	115
C5—H51⋯O1	0.97	2.51	3.095 (2)	119

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/S1600536809045851/hb5207sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045851/hb5207Isup2.hkl

checkCIF report

Comment top

Our group is involved in synthesizing various rhodanine derivatives for beta-lactamase and xanthine oxidase enzyme inhibition studies. In this context, we have already reported the preparation and 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), (IV) (5Z)-5-(2-Hydroxybenzylidene)-2-thioxo-1,3-thiazolidin-4-one methanol hemisolvate (Shahwar et al., 2009c) and (V) 3-(2-Methylphenyl)-2-thioxo-1,3-thiazolidin-4-one (Shahwar et al., 2009d). The title compound (I, Fig. 1) is in continuation of synthesizing rhodanine derivatives for biological studies.

In (I), the rhodanine group A (N1/C1/S1/C1/C3/O1/S2) and the basal plane B (C5/C6/C5ⁱ/C6ⁱ; symmetry code: i = x, - y + 1/2, z) of cyclohexyl are planar and are perpendicularly oriented. The monomeric molecules are stabilized through intramolecular H-bondings (Table 1, Fig. 1) forming a S(5) and two S(6) ring motifs (Bernstein et al., 1995). The apical C-atoms C4 and C7 of cyclohexyl are at a distance of 0.6430 (28) and -0.6667 (36) Å respectively, from the basal plane. There exist π–π interactions at a distance of 3.8140 (5) Å between the centroids of the heterocyclic rings.

Related literature top

For related structures, see: Shahwar et al. (2009a,b,c,d). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared by a three step reaction procedure. In the first step cyclohexylamine (9.9 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 clear 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 colourless 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 (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. The dotted lines represen the intramolecular H-bonds.

3-Cyclohexyl-2-thioxo-1,3-thiazolidin-4-one top

Crystal data top

C₉H₁₃NOS₂	F(000) = 228
M_r = 215.32	D_x = 1.382 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1390 reflections
a = 7.3897 (3) Å	θ = 2.9–28.4°
b = 7.0999 (4) Å	µ = 0.48 mm⁻¹
c = 10.3399 (5) Å	T = 296 K
β = 107.535 (2)°	Prism, colourless
V = 517.29 (4) Å³	0.36 × 0.25 × 0.23 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	1390 independent reflections
Radiation source: fine-focus sealed tube	1194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.4°, θ_min = 2.9°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −9→9
T_min = 0.849, T_max = 0.897	l = −13→12
5969 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0474P)² + 0.1418P] where P = (F_o² + 2F_c²)/3
1390 reflections	(Δ/σ)_max < 0.001
76 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₁₃NOS₂	V = 517.29 (4) Å³
M_r = 215.32	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.3897 (3) Å	µ = 0.48 mm⁻¹
b = 7.0999 (4) Å	T = 296 K
c = 10.3399 (5) Å	0.36 × 0.25 × 0.23 mm
β = 107.535 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1390 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1194 reflections with I > 2σ(I)
T_min = 0.849, T_max = 0.897	R_int = 0.028
5969 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.43 e Å⁻³
1390 reflections	Δρ_min = −0.23 e Å⁻³
76 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	0.01379 (9)	0.25000	0.58014 (6)	0.0511 (2)
S2	0.41214 (8)	0.25000	0.58341 (6)	0.0543 (2)
O1	−0.1794 (2)	0.25000	0.19333 (18)	0.0591 (6)
N1	0.1088 (2)	0.25000	0.35969 (16)	0.0351 (4)
C1	0.1866 (3)	0.25000	0.4967 (2)	0.0363 (5)
C2	−0.1778 (3)	0.25000	0.4253 (3)	0.0477 (7)
C3	−0.0908 (3)	0.25000	0.3109 (2)	0.0412 (6)
C4	0.2266 (2)	0.25000	0.26546 (19)	0.0356 (5)
C5	0.1971 (2)	0.0715 (2)	0.18098 (16)	0.0450 (4)
C6	0.3246 (2)	0.0739 (3)	0.08896 (17)	0.0527 (5)
C7	0.2925 (4)	0.25000	0.0025 (3)	0.0590 (8)
H2	−0.255 (2)	0.142 (3)	0.4183 (17)	0.0573*
H4	0.35945	0.25000	0.32201	0.0427*
H51	0.06529	0.06226	0.12627	0.0540*
H52	0.22695	−0.03748	0.24022	0.0540*
H61	0.45638	0.06820	0.14408	0.0633*
H62	0.29826	−0.03620	0.03070	0.0633*
H71	0.16366	0.25000	−0.05835	0.0707*
H72	0.37843	0.25000	−0.05230	0.0707*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0636 (4)	0.0480 (3)	0.0539 (3)	0.0000	0.0361 (3)	0.0000
S2	0.0461 (3)	0.0671 (4)	0.0438 (3)	0.0000	0.0046 (2)	0.0000
O1	0.0307 (7)	0.0850 (13)	0.0582 (10)	0.0000	0.0084 (7)	0.0000
N1	0.0300 (7)	0.0394 (8)	0.0382 (8)	0.0000	0.0138 (6)	0.0000
C1	0.0431 (9)	0.0288 (8)	0.0401 (10)	0.0000	0.0173 (8)	0.0000
C2	0.0417 (10)	0.0390 (11)	0.0722 (15)	0.0000	0.0318 (10)	0.0000
C3	0.0303 (8)	0.0395 (10)	0.0554 (12)	0.0000	0.0153 (8)	0.0000
C4	0.0273 (7)	0.0445 (10)	0.0365 (9)	0.0000	0.0121 (7)	0.0000
C5	0.0444 (7)	0.0422 (8)	0.0528 (8)	0.0012 (6)	0.0213 (6)	−0.0023 (6)
C6	0.0485 (8)	0.0602 (10)	0.0554 (9)	0.0028 (7)	0.0246 (7)	−0.0120 (8)
C7	0.0561 (13)	0.0816 (18)	0.0456 (12)	0.0000	0.0250 (10)	0.0000

Geometric parameters (Å, º) top

S1—C1	1.743 (2)	C6—C7	1.514 (3)
S1—C2	1.789 (3)	C2—H2	0.95 (2)
S2—C1	1.637 (2)	C2—H2ⁱ	0.95 (2)
O1—C3	1.195 (3)	C4—H4	0.9800
N1—C1	1.359 (3)	C5—H51	0.9700
N1—C3	1.408 (3)	C5—H52	0.9700
N1—C4	1.489 (2)	C6—H61	0.9700
C2—C3	1.507 (3)	C6—H62	0.9700
C4—C5	1.5172 (18)	C7—H71	0.9700
C4—C5ⁱ	1.5172 (18)	C7—H72	0.9700
C5—C6	1.528 (2)

C1—S1—C2	93.28 (11)	C3—C2—H2ⁱ	109.3 (10)
C1—N1—C3	116.24 (17)	H2—C2—H2ⁱ	108.4 (16)
C1—N1—C4	122.34 (16)	N1—C4—H4	107.00
C3—N1—C4	121.43 (15)	C5—C4—H4	107.00
S1—C1—S2	120.37 (12)	C5ⁱ—C4—H4	107.00
S1—C1—N1	111.90 (16)	C4—C5—H51	110.00
S2—C1—N1	127.73 (17)	C4—C5—H52	110.00
S1—C2—C3	107.02 (16)	C6—C5—H51	110.00
O1—C3—N1	124.0 (2)	C6—C5—H52	110.00
O1—C3—C2	124.5 (2)	H51—C5—H52	108.00
N1—C3—C2	111.56 (18)	C5—C6—H61	109.00
N1—C4—C5	111.45 (9)	C5—C6—H62	109.00
N1—C4—C5ⁱ	111.45 (9)	C7—C6—H61	109.00
C5—C4—C5ⁱ	113.30 (14)	C7—C6—H62	109.00
C4—C5—C6	109.92 (13)	H61—C6—H62	108.00
C5—C6—C7	111.15 (17)	C6—C7—H71	109.00
C6—C7—C6ⁱ	111.4 (2)	C6—C7—H72	109.00
S1—C2—H2	111.4 (11)	H71—C7—H72	108.00
S1—C2—H2ⁱ	111.4 (11)	C6ⁱ—C7—H71	109.00
C3—C2—H2	109.3 (10)	C6ⁱ—C7—H72	109.00

C2—S1—C1—S2	180.00 (1)	C4—N1—C3—C2	180.00 (1)
C2—S1—C1—N1	0.00 (1)	C1—N1—C4—C5	116.17 (11)
C1—S1—C2—C3	0.00 (1)	C3—N1—C4—C5	−63.83 (11)
C3—N1—C1—S1	0.00 (1)	S1—C2—C3—O1	180.00 (1)
C3—N1—C1—S2	180.00 (1)	S1—C2—C3—N1	0.00 (1)
C4—N1—C1—S1	180.00 (1)	N1—C4—C5—C6	−178.24 (13)
C4—N1—C1—S2	0.00 (1)	C5ⁱ—C4—C5—C6	55.10 (17)
C1—N1—C3—O1	180.00 (1)	C4—C5—C6—C7	−54.99 (19)
C1—N1—C3—C2	0.00 (1)	C5—C6—C7—C6ⁱ	56.9 (2)
C4—N1—C3—O1	0.00 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···S2	0.98	2.61	3.158 (2)	115
C5—H51···O1	0.97	2.51	3.095 (2)	119

Experimental details

Crystal data
Chemical formula	C₉H₁₃NOS₂
M_r	215.32
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	296
a, b, c (Å)	7.3897 (3), 7.0999 (4), 10.3399 (5)
β (°)	107.535 (2)
V (Å³)	517.29 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.36 × 0.25 × 0.23

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	5969, 1390, 1194
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.096, 1.07
No. of reflections	1390
No. of parameters	76
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.23

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
C4—H4···S2	0.98	2.61	3.158 (2)	115
C5—H51···O1	0.97	2.51	3.095 (2)	119

Acknowledgements

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

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
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
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