rac-5-(1-Methyl­eth­yl)-2-sulfanylidene­imidazolidin-4-one

Castro, R. de P.; Macedo Jr, F.C.; Brito, T.O.; Fátima, A. de; Sabino, J.R.

doi:10.1107/S1600536813008337

organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Page o643

https://doi.org/10.1107/S1600536813008337

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rac-5-(1-Methylethyl)-2-sulfanylideneimidazolidin-4-one

Rosane de P. Castro,^a ^* Fernando C. Macedo Jr,^b Tiago O. Brito,^b Angelo de Fátima ^c and José R. Sabino ^a

^aInstituto de Física – UFG, Caixa Postal 131, 74001-970 Goiânia, GO, Brazil, ^bDepartamento de Química – UEL, Caixa Postal 6001, 86051-990 Londrina, PR, Brazil, and ^cDepartamento de Química – UFMG, 31270-901 - Belo Horizonte, MG, Brazil
^*Correspondence e-mail: rosanepc@posgrad.ufg.br

(Received 18 March 2013; accepted 26 March 2013; online 5 April 2013)

In the title compound, C₆H₁₀N₂OS, the 2-sulfanylideneimidazolidin-4-one fragment is essentially planar (r.m.s. deviation = 0.0033 Å). In the crystal, one amino group is involved in N—H⋯O hydrogen bonding, which links pairs of molecules into inversion dimers, while the other amino group generates weak N—H⋯S hydrogen bonds, which link these dimers into chains in [10-1]. The chains are further aggregated into layers parallel to the ac plane through weak C—H⋯O interactions.

Related literature

For the biological activity of 2-thiohydantoin derivatives, see: Ghoneim et al. (1987 ); Marton et al. (1993 ). For the crystal structures of related compounds, see: Kunimoto et al. (2009 ); Ogawa et al. (2007 ). For details of the synthesis, see: Wang et al. (2006 ).

Experimental

Crystal data

C₆H₁₀N₂OS
M_r = 158.23
Monoclinic, P 2₁ /c
a = 5.7161 (1) Å
b = 17.4091 (4) Å
c = 8.2505 (2) Å
β = 103.513 (1)°
V = 798.30 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 308 K
0.93 × 0.4 × 0.3 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.936, T_max = 0.979
18741 measured reflections
3064 independent reflections
2544 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.114
S = 1.02
3064 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.02	2.8573 (11)	164
N1—H1⋯S1ⁱⁱ	0.86	2.52	3.3806 (9)	176
C6—H6C⋯O1ⁱⁱⁱ	0.96	2.52	3.4434 (14)	160
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z; (iii) x+1, y, z.

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); 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, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813008337/cv5395sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008337/cv5395Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813008337/cv5395Isup3.cml

checkCIF report

Comment top

2-Thiohydantoin derivatives demonstrate biological activities when used as drugs, fungicides and herbicides (Ghoneim et al., 1987; Marton et al., 1993). Herewith we present the title compound, (I), which is a new 2-thiohydantoin derivative.

In (I) (Fig. 1), the thiohydantoin ring is essentially planar [r.m.s = 0.0033 Å and largest deviation of 0.008 (2) Å for O1]. The orientation of the isopropyl group, defined by the atoms C4, C5 and C6, relative to this plane is given by the torsion angles N1—C3—C4—C5 and N1—C3—C4—C6 of 169.42 (9) and 65.8 (1)°, respectively. The C1—S1 bond, 1.6621 (9), has double-bond character. The N2—C1 bond distance is longer than N1—C1 bond distance by 0.047 Å. The N1—C1—S1 bond angle is greater than N2—C1—S1 bond angle by 3.84°. These differences are also observed in two similar compounds: 5-phenyl-2-sulfanylidene-4-imidazolidinone [CSD refcode: YINGIM (Ogawa et al., 2007)] and rac-5-benzyl-2-thiohydantoin [CSD refcode: KUGDUM (Kunimoto et al., 2009)]. Besides, the molecular geometry of the title compound is comparable to these reference molecules within the standard uncertainties.

Intermolecular N—H···O hydrogen bonds (Table 1) lead to centrosymmetric dimers formation. Weak interactions of type N—H···S (Table 1) mediate the formation of the chains along [101], which are further linked into layers parallel to ac plane through the weak C—H···O interactions (Table 1).

Related literature top

For the biological activity of 2-thiohydantoin derivatives, see: Ghoneim et al. (1987); Marton et al. (1993). For the crystal structures of related compounds, see: Kunimoto et al. (2009); Ogawa et al. (2007). For details of the synthesis, see: Wang et al. (2006).

Experimental top

The procedure employed for synthesis of compound (I) was described by Wang et al. (2006). A mixture of D-valine (2.34 g, 0.2 mol) and thiourea (4.57 g, 0.6 mol) was added in a flask and heated under stirring. The reaction was remained in the oil bath at temperature of 190°C for 30 minutes, after this period, the flask was allowed to cool down and water (20 ml) was added while the flask was still warm. The solution was reheated to dissolve all the solids and allowed to cool to room temperature, then placed in a refrigerator for 3 h. The solid were removed by vacuum filtration and storage. Recrystallization from chloroform yielded single crystals suitable for X-ray analysis.

Structure description top

For the biological activity of 2-thiohydantoin derivatives, see: Ghoneim et al. (1987); Marton et al. (1993). For the crystal structures of related compounds, see: Kunimoto et al. (2009); Ogawa et al. (2007). For details of the synthesis, see: Wang et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The structure structure of (I) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level
	Fig. 2. A portion of the crystal packing, showing intermolecular hydrogen bonds as dashed lines [symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z].

rac-5-(1-Methylethyl)-2-sulfanylideneimidazolidin-4-one top

Crystal data top

C₆H₁₀N₂OS	F(000) = 336
M_r = 158.23	D_x = 1.316 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 637 reflections
a = 5.7161 (1) Å	θ = 7.0–60.8°
b = 17.4091 (4) Å	µ = 0.34 mm⁻¹
c = 8.2505 (2) Å	T = 308 K
β = 103.513 (1)°	Prism, colourless
V = 798.30 (3) Å³	0.93 × 0.4 × 0.3 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2544 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.020
φ and ω scans	θ_max = 34.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −9→8
T_min = 0.936, T_max = 0.979	k = −26→27
18741 measured reflections	l = −12→13
3064 independent 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0671P)² + 0.0869P] where P = (F_o² + 2F_c²)/3
3064 reflections	(Δ/σ)_max = 0.002
93 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₆H₁₀N₂OS	V = 798.30 (3) Å³
M_r = 158.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.7161 (1) Å	µ = 0.34 mm⁻¹
b = 17.4091 (4) Å	T = 308 K
c = 8.2505 (2) Å	0.93 × 0.4 × 0.3 mm
β = 103.513 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3064 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	2544 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.979	R_int = 0.020
18741 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.02	Δρ_max = 0.33 e Å⁻³
3064 reflections	Δρ_min = −0.20 e Å⁻³
93 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

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 > 2σ(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	0.50440 (6)	0.579973 (16)	0.22144 (4)	0.04944 (11)
C1	0.31293 (17)	0.50804 (5)	0.22060 (11)	0.03529 (18)
N1	0.25674 (18)	0.45108 (5)	0.11098 (10)	0.0431 (2)
H1	0.3188	0.446	0.0262	0.052*
C3	0.07920 (18)	0.39803 (6)	0.14899 (11)	0.03667 (18)
H3	−0.0682	0.4005	0.0602	0.044*
C4	0.16814 (19)	0.31474 (5)	0.16973 (13)	0.0415 (2)
H4	0.2276	0.3015	0.0711	0.05*
C5	−0.0352 (2)	0.25955 (7)	0.17693 (18)	0.0568 (3)
H5A	−0.0905	0.2689	0.2764	0.085*
H5B	0.0219	0.2077	0.1778	0.085*
H5C	−0.1655	0.2672	0.0811	0.085*
C6	0.3773 (2)	0.30522 (7)	0.3219 (2)	0.0595 (3)
H6C	0.5011	0.3417	0.3163	0.089*
H6B	0.4408	0.2541	0.3236	0.089*
H6A	0.3215	0.3139	0.4214	0.089*
C2	0.03374 (17)	0.43453 (5)	0.30588 (12)	0.03636 (18)
O1	−0.10205 (16)	0.41213 (5)	0.38922 (12)	0.0516 (2)
N2	0.17754 (15)	0.49851 (5)	0.33699 (11)	0.03987 (18)
H2	0.1825	0.5291	0.4196	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0669 (2)	0.04239 (16)	0.04620 (17)	−0.02026 (11)	0.02773 (13)	−0.00744 (10)
C1	0.0445 (4)	0.0311 (4)	0.0333 (4)	−0.0024 (3)	0.0153 (3)	0.0008 (3)
N1	0.0626 (5)	0.0386 (4)	0.0348 (4)	−0.0127 (4)	0.0248 (4)	−0.0050 (3)
C3	0.0431 (4)	0.0368 (4)	0.0320 (4)	−0.0061 (3)	0.0126 (3)	−0.0032 (3)
C4	0.0497 (5)	0.0335 (4)	0.0486 (5)	−0.0080 (4)	0.0263 (4)	−0.0118 (4)
C5	0.0625 (7)	0.0448 (6)	0.0676 (7)	−0.0212 (5)	0.0242 (6)	−0.0143 (5)
C6	0.0440 (5)	0.0419 (5)	0.0917 (10)	0.0023 (4)	0.0142 (6)	0.0060 (6)
C2	0.0379 (4)	0.0328 (4)	0.0431 (4)	−0.0009 (3)	0.0190 (3)	−0.0048 (3)
O1	0.0562 (5)	0.0449 (4)	0.0667 (5)	−0.0122 (3)	0.0406 (4)	−0.0155 (4)
N2	0.0486 (4)	0.0345 (4)	0.0431 (4)	−0.0074 (3)	0.0239 (3)	−0.0096 (3)

Geometric parameters (Å, º) top

S1—C1	1.6621 (9)	C4—H4	0.98
C1—N1	1.3300 (12)	C5—H5A	0.96
C1—N2	1.3769 (12)	C5—H5B	0.96
N1—C3	1.4595 (12)	C5—H5C	0.96
N1—H1	0.86	C6—H6C	0.96
C3—C2	1.5179 (13)	C6—H6B	0.96
C3—C4	1.5328 (14)	C6—H6A	0.96
C3—H3	0.98	C2—O1	1.2152 (12)
C4—C5	1.5200 (14)	C2—N2	1.3724 (12)
C4—C6	1.5269 (18)	N2—H2	0.86

N1—C1—N2	107.37 (8)	C4—C5—H5A	109.5
N1—C1—S1	128.23 (7)	C4—C5—H5B	109.5
N2—C1—S1	124.39 (7)	H5A—C5—H5B	109.5
C1—N1—C3	113.28 (8)	C4—C5—H5C	109.5
C1—N1—H1	123.4	H5A—C5—H5C	109.5
C3—N1—H1	123.4	H5B—C5—H5C	109.5
N1—C3—C2	100.63 (7)	C4—C6—H6C	109.5
N1—C3—C4	113.17 (8)	C4—C6—H6B	109.5
C2—C3—C4	114.79 (8)	H6C—C6—H6B	109.5
N1—C3—H3	109.3	C4—C6—H6A	109.5
C2—C3—H3	109.3	H6C—C6—H6A	109.5
C4—C3—H3	109.3	H6B—C6—H6A	109.5
C5—C4—C6	111.00 (10)	O1—C2—N2	126.04 (9)
C5—C4—C3	111.44 (9)	O1—C2—C3	127.40 (9)
C6—C4—C3	111.72 (8)	N2—C2—C3	106.55 (8)
C5—C4—H4	107.5	C2—N2—C1	112.15 (8)
C6—C4—H4	107.5	C2—N2—H2	123.9
C3—C4—H4	107.5	C1—N2—H2	123.9

N2—C1—N1—C3	−0.87 (12)	N1—C3—C2—O1	−179.83 (11)
S1—C1—N1—C3	−179.62 (7)	C4—C3—C2—O1	−57.99 (15)
C1—N1—C3—C2	0.55 (11)	N1—C3—C2—N2	−0.03 (10)
C1—N1—C3—C4	−122.43 (10)	C4—C3—C2—N2	121.82 (9)
N1—C3—C4—C5	−169.42 (9)	O1—C2—N2—C1	179.33 (11)
C2—C3—C4—C5	75.83 (11)	C3—C2—N2—C1	−0.49 (11)
N1—C3—C4—C6	65.78 (11)	N1—C1—N2—C2	0.84 (12)
C2—C3—C4—C6	−48.97 (12)	S1—C1—N2—C2	179.65 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.02	2.8573 (11)	164
N1—H1···S1ⁱⁱ	0.86	2.52	3.3806 (9)	176
C6—H6C···O1ⁱⁱⁱ	0.96	2.52	3.4434 (14)	160

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₆H₁₀N₂OS
M_r	158.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	308
a, b, c (Å)	5.7161 (1), 17.4091 (4), 8.2505 (2)
β (°)	103.513 (1)
V (Å³)	798.30 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.93 × 0.4 × 0.3

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2010)
T_min, T_max	0.936, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	18741, 3064, 2544
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.792

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.114, 1.02
No. of reflections	3064
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.20

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.02	2.8573 (11)	163.8
N1—H1···S1ⁱⁱ	0.86	2.52	3.3806 (9)	175.5
C6—H6C···O1ⁱⁱⁱ	0.96	2.52	3.4434 (14)	160.3

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x+1, y, z.

Acknowledgements

This work includes part of the activities developed by the Network of Studies and the Development of Novel Inhibitors of Urease, financed by CNPq (562479/2010–4) and FAPEMIG (APQ-04781–10). The authors are also grateful to CNPq (TOB) and CAPES (RPC) for providing their respective fellowships.

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