5-Eth­oxy-1,3,4-thia­diazole-2(3H)-thione

Kang, S.K.; Cho, N.S.; Jang, S.

doi:10.1107/S1600536812002024

organic compounds

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5-Ethoxy-1,3,4-thiadiazole-2(3H)-thione

Sung Kwon Kang,^a ^* Nam Sook Cho ^a and Siyoung Jang ^a

^aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

(Received 15 January 2012; accepted 17 January 2012; online 21 January 2012)

In the title compound, C₄H₆N₂OS₂, the dihedral angle between the five-membered heterocyclic ring and the plane of the ethoxy group is 4.9 (2)°. The 1,3,4-thiadiazole-2-thione unit is planar, with an r.m.s. deviation of 0.011 Å from the corresponding squares plane defined by the seven constituent atoms. In the crystal, pairs of N—H⋯S hydrogen bonds link the molecules into inversion dimers.

Related literature

For the synthesis and reactivity of thiadiazole derivatives, see: Hildebrandt et al. (2011 ); Zhan et al. (2009 ); Cho et al. (1998 ); Squillacote & Felippis (1994 ); Antolini et al. (1993 ).

Experimental

Crystal data

C₄H₆N₂OS₂
M_r = 162.23
Triclinic, $[P \overline 1]$
a = 6.0308 (12) Å
b = 8.1171 (16) Å
c = 8.7616 (18) Å
α = 116.55 (4)°
β = 93.70 (3)°
γ = 106.10 (3)°
V = 359.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 296 K
0.16 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.905, T_max = 0.951
10973 measured reflections
1329 independent reflections
1020 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.106
S = 1.03
1329 reflections
86 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯S6ⁱ	0.76 (2)	2.57 (2)	3.317 (3)	170 (3)
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812002024/is5053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002024/is5053Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812002024/is5053Isup3.cml

checkCIF report

Comment top

Thiadiazole derivatives have recently attracted attention in synthesis and biological activities (Hildebrandt et al., 2011; Zhan et al., 2009). 1,2,4-Thiadiazolidine-3,5-dione is a 5-membered analog of uracil on the basis of the well known subject between a –CH=CH– group in benzenoid hydrocarbons and the divalent sulfur in its sulfur containing counterparts. 5-Thioxo-1,3,4-thiadiazolidin-2-one is an analog of 1,2,4-thiadiazolidine-3,5-dione (Squillacote & Felippis, 1994; Antolini et al., 1993). Derivatives of 5-thioxo-1,3,4-thiadiazolidin-2-one have potential to have biological activities. The title compound, 5-ethoxy-3H-1,3,4-thiadiazoline-2-thione (I) is an intermediate to prepare 3-thioxo-1,3,4-thiadiazolidin-2-one through hydrolysis. However, the hydrolysis afforded bis(2-oxo-3H-1,3,4-thiadiazolinyl)-5,5'-disulfide which is a oxidative dimer of 5-thioxo-1,3,4-thiadiazolidin-2-one (Cho et al., 1998)

The 1,3,4-thiadiazole-2-thione unit is planar, with an r.m.s. deviation of 0.011 Å from the corresponding squares plane defined by the seven constituent atoms. The bond distance of N4—C5 [1.293 (3) Å] is shorter than that of C2—N3 [1.325 (3) Å], which is consistent with double bond character. The intermolecular N3—H3···S6ⁱ [symmetry code: (i) -x, -y + 1, -z + 1] hydrogen bonds link two molecules into a centrosymmetric dimer (Fig. 2 and Table 1), which stabilize the crystal structure.

Related literature top

For the synthesis and reactivity of thiadiazole derivatives, see: Hildebrandt et al. (2011); Zhan et al. (2009); Cho et al. (1998); Squillacote & Felippis (1994); Antolini et al. (1993).

Experimental top

Ethyl thiocarbazinate (11.6 g, 0.1 mol) was dissolved in CS₂ (6.5 ml, 0.11 mol). KOH (0.86 g, 18 mmol) in 20 ml of methyl alcohol was added to the above solution and it was refluxed for 6 h. The reaction mixture was cooled to room temperature and distilled off the solvent under reduced pressure. The resulting residue was dispersed in 20 ml water and acidified with c-HCl (9 ml). Product was collected (8.0 g, 51% yield) and recrystallized in benzene to obtain the analytical sample. Colourless crystals of (I) were obtained from its ethanol solution by slow evaporation of the solvent at room temperature. mp 128–130 °C, Rf, 0.48 (hexane: ethyl acetate = 7: 3 v/v); IR (KBr, cm^-1) 3100 (NH), 2850 (CH), 1560 (C=N), 1350. ¹H NMR (CDCl₃, p.p.m.) 13.7 (1H, b, NH), 4.4 (2H, q, CH₂), 1.4 (3H, t, CH₃).; ¹³C NMR (CDCl₃, p.p.m.) 184.2 (C=S), 165.6 (C—O), 69.0 (CH₂), 14.0 (CH₃). Anal. Calcd. for C₄H₆N₂OS₂: C 29.62, H 3.73, N 17.27. Found: C 29.75, H 3.58, N 16.56.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids.
	Fig. 2. Part of the crystal structure of the title compound, showing molecules linked by intermolecular N—H···S hydrogen bonds (dashed lines).

5-Ethoxy-1,3,4-thiadiazole-2(3H)-thione top

Crystal data top

C₄H₆N₂OS₂	Z = 2
M_r = 162.23	F(000) = 168
Triclinic, P1	D_x = 1.498 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0308 (12) Å	Cell parameters from 3632 reflections
b = 8.1171 (16) Å	θ = 2.9–24.6°
c = 8.7616 (18) Å	µ = 0.66 mm⁻¹
α = 116.55 (4)°	T = 296 K
β = 93.70 (3)°	Block, colourless
γ = 106.10 (3)°	0.16 × 0.12 × 0.08 mm
V = 359.7 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1020 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ϕ and ω scans	θ_max = 25.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→7
T_min = 0.905, T_max = 0.951	k = −9→9
10973 measured reflections	l = −10→10
1329 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0692P)²] where P = (F_o² + 2F_c²)/3
1329 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₄H₆N₂OS₂	γ = 106.10 (3)°
M_r = 162.23	V = 359.7 (2) Å³
Triclinic, P1	Z = 2
a = 6.0308 (12) Å	Mo Kα radiation
b = 8.1171 (16) Å	µ = 0.66 mm⁻¹
c = 8.7616 (18) Å	T = 296 K
α = 116.55 (4)°	0.16 × 0.12 × 0.08 mm
β = 93.70 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1329 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1020 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.951	R_int = 0.078
10973 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.34 e Å⁻³
1329 reflections	Δρ_min = −0.25 e Å⁻³
86 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > 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	0.58072 (11)	0.69466 (8)	0.86851 (8)	0.0633 (3)
C2	0.3257 (4)	0.6379 (3)	0.7233 (3)	0.0478 (5)
N3	0.2660 (4)	0.4510 (3)	0.6039 (3)	0.0522 (5)
H3	0.158 (4)	0.408 (4)	0.531 (3)	0.055 (8)*
N4	0.3981 (3)	0.3405 (3)	0.6130 (3)	0.0523 (5)
C5	0.5704 (4)	0.4537 (3)	0.7487 (3)	0.0500 (6)
S6	0.18884 (11)	0.79469 (9)	0.73697 (8)	0.0591 (3)
O7	0.7344 (3)	0.4010 (2)	0.8031 (2)	0.0623 (5)
C8	0.7080 (5)	0.1955 (3)	0.7051 (3)	0.0572 (6)
H8A	0.7218	0.1607	0.5857	0.069*
H8B	0.5544	0.1142	0.7027	0.069*
C9	0.9014 (5)	0.1656 (4)	0.7956 (4)	0.0711 (7)
H9A	0.89	0.0306	0.7338	0.107*
H9B	0.8853	0.1999	0.9133	0.107*
H9C	1.0524	0.2471	0.7974	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0619 (4)	0.0459 (4)	0.0679 (4)	0.0255 (3)	−0.0096 (3)	0.0151 (3)
C2	0.0472 (12)	0.0499 (13)	0.0521 (12)	0.0229 (10)	0.0101 (10)	0.0260 (10)
N3	0.0476 (11)	0.0498 (11)	0.0560 (12)	0.0221 (9)	−0.0011 (10)	0.0215 (9)
N4	0.0525 (11)	0.0445 (10)	0.0592 (11)	0.0241 (9)	0.0025 (9)	0.0216 (9)
C5	0.0480 (13)	0.0453 (12)	0.0593 (14)	0.0223 (10)	0.0042 (11)	0.0249 (11)
S6	0.0597 (4)	0.0531 (4)	0.0668 (4)	0.0319 (3)	0.0059 (3)	0.0248 (3)
O7	0.0583 (10)	0.0458 (9)	0.0739 (11)	0.0241 (8)	−0.0102 (8)	0.0214 (8)
C8	0.0620 (15)	0.0471 (13)	0.0634 (14)	0.0263 (11)	0.0047 (11)	0.0243 (11)
C9	0.0803 (19)	0.0673 (17)	0.0799 (18)	0.0429 (14)	0.0091 (14)	0.0382 (14)

Geometric parameters (Å, º) top

S1—C5	1.738 (2)	O7—C8	1.449 (3)
S1—C2	1.740 (2)	C8—C9	1.502 (3)
C2—N3	1.325 (3)	C8—H8A	0.97
C2—S6	1.665 (2)	C8—H8B	0.97
N3—N4	1.377 (3)	C9—H9A	0.96
N3—H3	0.76 (2)	C9—H9B	0.96
N4—C5	1.293 (3)	C9—H9C	0.96
C5—O7	1.321 (2)

C5—S1—C2	89.00 (11)	O7—C8—C9	107.07 (19)
N3—C2—S6	127.91 (18)	O7—C8—H8A	110.3
N3—C2—S1	107.12 (17)	C9—C8—H8A	110.3
S6—C2—S1	124.97 (15)	O7—C8—H8B	110.3
C2—N3—N4	120.52 (19)	C9—C8—H8B	110.3
C2—N3—H3	118 (2)	H8A—C8—H8B	108.6
N4—N3—H3	121 (2)	C8—C9—H9A	109.5
C5—N4—N3	107.33 (18)	C8—C9—H9B	109.5
N4—C5—O7	125.7 (2)	H9A—C9—H9B	109.5
N4—C5—S1	116.01 (17)	C8—C9—H9C	109.5
O7—C5—S1	118.33 (16)	H9A—C9—H9C	109.5
C5—O7—C8	115.95 (17)	H9B—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S6ⁱ	0.76 (2)	2.57 (2)	3.317 (3)	170 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₄H₆N₂OS₂
M_r	162.23
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.0308 (12), 8.1171 (16), 8.7616 (18)
α, β, γ (°)	116.55 (4), 93.70 (3), 106.10 (3)
V (Å³)	359.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.16 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.905, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	10973, 1329, 1020
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.106, 1.03
No. of reflections	1329
No. of parameters	86
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.25

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S6ⁱ	0.76 (2)	2.57 (2)	3.317 (3)	170 (3)

Symmetry code: (i) −x, −y+1, −z+1.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o503

doi:10.1107/S1600536812002024

Open

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