5-Meth­oxy-1,3,4-thia­diazol-2(3H)-one

Zhang, W.-Y.; Liu, J.; Liu, Y.-J.

doi:10.1107/S160053681200178X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o475

doi:10.1107/S160053681200178X

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5-Methoxy-1,3,4-thiadiazol-2(3H)-one

Wei-Yi Zhang,^a Jie Liu ^b ^* and Yan-Ju Liu ^c

^aDepartment of Obstetrics and Gynecology, The First Affiliated Hospital of Henan University of Traditional Chinese, Medicine, Zhengzhou 450008, People's Republic of China, ^bDepartment of Urology, Henan Provincial People's Hospital, Zhengzhou 450003, People's Republic of China, and ^cPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: liuyanju886@163.com

(Received 3 January 2012; accepted 15 January 2012; online 21 January 2012)

The three molecules in the asymmetric unit of the title compound, C₃H₄N₂O₂S, are connected via N—H⋯O hydrogen bonds, forming layers normal to [001]. The rings of the molecules are approximately planar, with r.m.s. deviations of 0.0051 (1), 0.0044 (1) and 0.0111 (1) Å.

Related literature

For background to the applications of the title compound, see: Collier (2004 ). For the synthesis, see: Zhu et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₃H₄N₂O₂S
M_r = 132.16
Hexagonal, P 6₁
a = 11.9240 (17) Å
c = 20.111 (4) Å
V = 2476.3 (7) Å³
Z = 18
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.867, T_max = 0.909
3492 measured reflections
3040 independent reflections
2206 reflections with I > 2σ(I)
R_int = 0.039
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.133
S = 1.04
3040 reflections
217 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.38 e Å⁻³
Absolute structure: Flack (1983 ), 1468 Friedel pairs
Flack parameter: −0.05 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.86	1.97	2.796 (7)	160
N3—H3D⋯O5	0.86	1.96	2.788 (6)	161
N5—H5A⋯O1ⁱⁱ	0.86	1.99	2.813 (8)	161
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200178X/bq2331sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200178X/bq2331Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200178X/bq2331Isup3.cml

checkCIF report

Comment top

The tittle compound, 2-methoxythiazol-5(4H)-one is an important intermediate, which can be utilized to synthesize herbicide fluthiacet-ethyl (Collier, 2004). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. In the crystal structure, the asymmetric unit contains three molecules of 2-methoxythiazol-5(4H)-one and these molecules were connected together via N-H···O intermolecular hydrogen bonds forming stacking layers along c-axis (Fig. 2.). In the crystal structure, the rings are planar, with r.m.s. deviation of 0.06 (1) Å. The bond lengths and angles are within normal ranges (Allen et al., 1987).

Related literature top

For background to the applications of the title compound, see: Collier (2004). For the synthesis, see: Zhu et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Zhu et al., 2011). The crystals were obtained by dissolving (I) (0.2 g) in methanol (50 ml) and evaporating the solvent slowly at room temperature for about 10 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intermolecular H-bonds are shown with dashed lines.
	Fig. 2. A packing diagram of (I) showing the stacked layers along c-axis.

5-Methoxy-1,3,4-thiadiazol-2(3H)-one top

Crystal data top

C₃H₄N₂O₂S	D_x = 1.595 Mg m⁻³
M_r = 132.16	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₁	Cell parameters from 25 reflections
Hall symbol: P 61	θ = 9–13°
a = 11.9240 (17) Å	µ = 0.49 mm⁻¹
c = 20.111 (4) Å	T = 293 K
V = 2476.3 (7) Å³	Block, colourless
Z = 18	0.30 × 0.20 × 0.20 mm
F(000) = 1224

Data collection top

Enraf–Nonius CAD-4 diffractometer	2206 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
Graphite monochromator	θ_max = 25.4°, θ_min = 2.0°
ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.867, T_max = 0.909	l = −24→24
3492 measured reflections	3 standard reflections every 200 reflections
3040 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.056	w = 1/[σ²(F_o²) + (0.0696P)² + 0.1426P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.133	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.27 e Å⁻³
3040 reflections	Δρ_min = −0.38 e Å⁻³
217 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
1 restraint	Extinction coefficient: 0.0009 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1468 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.05 (14)

Crystal data top

C₃H₄N₂O₂S	Z = 18
M_r = 132.16	Mo Kα radiation
Hexagonal, P6₁	µ = 0.49 mm⁻¹
a = 11.9240 (17) Å	T = 293 K
c = 20.111 (4) Å	0.30 × 0.20 × 0.20 mm
V = 2476.3 (7) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	2206 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.039
T_min = 0.867, T_max = 0.909	3 standard reflections every 200 reflections
3492 measured reflections	intensity decay: 1%
3040 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.133	Δρ_max = 0.27 e Å⁻³
S = 1.04	Δρ_min = −0.38 e Å⁻³
3040 reflections	Absolute structure: Flack (1983), 1468 Friedel pairs
217 parameters	Absolute structure parameter: −0.05 (14)
1 restraint

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	0.82079 (12)	0.67453 (12)	0.52166 (9)	0.0559 (4)
N1	0.8459 (4)	0.4789 (4)	0.5285 (3)	0.0500 (12)
H1A	0.8783	0.4288	0.5317	0.060*
C1	0.9238 (5)	0.6063 (5)	0.5255 (3)	0.0473 (14)
O1	1.0407 (3)	0.6672 (4)	0.5228 (3)	0.0709 (14)
N2	0.7133 (4)	0.4265 (4)	0.5265 (3)	0.0487 (12)
O2	0.5724 (3)	0.5049 (3)	0.5201 (2)	0.0638 (12)
C2	0.6895 (5)	0.5184 (5)	0.5232 (3)	0.0440 (13)
C3	0.4662 (5)	0.3737 (6)	0.5148 (4)	0.071 (2)
H3A	0.3860	0.3742	0.5130	0.107*
H3B	0.4659	0.3248	0.5528	0.107*
H3C	0.4759	0.3348	0.4751	0.107*
S2	−0.10862 (12)	0.04825 (12)	0.51466 (7)	0.0452 (4)
O3	−0.1023 (4)	0.2749 (4)	0.5220 (3)	0.0646 (12)
O4	0.0620 (3)	−0.0301 (3)	0.5161 (2)	0.0564 (11)
N3	0.0884 (4)	0.2708 (4)	0.5190 (3)	0.0497 (12)
H3D	0.1382	0.3535	0.5191	0.060*
N4	0.1407 (4)	0.1911 (4)	0.5184 (3)	0.0443 (11)
C4	−0.0410 (5)	0.2188 (5)	0.5194 (3)	0.0431 (13)
C5	0.0477 (4)	0.0735 (5)	0.5165 (3)	0.0429 (12)
C6	0.1950 (5)	−0.0021 (6)	0.5226 (4)	0.0588 (16)
H6A	0.1968	−0.0817	0.5216	0.088*
H6B	0.2302	0.0416	0.5640	0.088*
H6C	0.2456	0.0521	0.4864	0.088*
S3	0.52008 (12)	0.74536 (12)	0.53340 (7)	0.0513 (4)
O5	0.2932 (4)	0.5245 (3)	0.5299 (3)	0.0760 (14)
O6	0.5965 (3)	0.9929 (3)	0.5329 (2)	0.0622 (12)
N5	0.2976 (4)	0.7178 (4)	0.5261 (3)	0.0519 (12)
H5A	0.2149	0.6839	0.5233	0.062*
N6	0.3771 (4)	0.8501 (4)	0.5268 (3)	0.0500 (11)
C7	0.3507 (5)	0.6438 (5)	0.5296 (3)	0.0486 (14)
C8	0.4939 (4)	0.8748 (5)	0.5309 (3)	0.0447 (13)
C9	0.5707 (6)	1.0982 (5)	0.5339 (5)	0.074 (2)
H9A	0.6511	1.1787	0.5356	0.111*
H9B	0.5198	1.0907	0.5725	0.111*
H9C	0.5240	1.0955	0.4945	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0353 (7)	0.0322 (7)	0.1008 (12)	0.0171 (6)	0.0044 (9)	0.0039 (8)
N1	0.038 (2)	0.035 (2)	0.082 (4)	0.023 (2)	−0.001 (3)	−0.003 (3)
C1	0.034 (3)	0.039 (3)	0.069 (4)	0.019 (3)	0.003 (3)	−0.004 (3)
O1	0.033 (2)	0.050 (2)	0.125 (4)	0.0174 (18)	0.004 (3)	−0.004 (3)
N2	0.035 (2)	0.035 (2)	0.076 (4)	0.0171 (19)	0.001 (2)	0.000 (3)
O2	0.0308 (18)	0.043 (2)	0.117 (4)	0.0178 (16)	0.004 (2)	−0.003 (3)
C2	0.031 (2)	0.033 (3)	0.066 (4)	0.014 (2)	0.008 (3)	0.007 (3)
C3	0.036 (3)	0.053 (4)	0.115 (7)	0.015 (3)	−0.006 (4)	−0.011 (4)
S2	0.0315 (6)	0.0334 (6)	0.0664 (9)	0.0132 (5)	−0.0002 (6)	−0.0008 (6)
O3	0.059 (3)	0.047 (2)	0.101 (3)	0.036 (2)	−0.005 (3)	−0.004 (2)
O4	0.045 (2)	0.0305 (19)	0.096 (3)	0.0208 (16)	−0.003 (2)	−0.001 (2)
N3	0.042 (2)	0.025 (2)	0.079 (4)	0.0145 (18)	−0.006 (3)	0.001 (2)
N4	0.035 (2)	0.029 (2)	0.066 (3)	0.0139 (17)	0.000 (3)	0.004 (2)
C4	0.043 (3)	0.031 (2)	0.057 (4)	0.020 (2)	−0.002 (3)	0.000 (3)
C5	0.038 (3)	0.037 (3)	0.052 (3)	0.017 (2)	0.002 (3)	0.003 (3)
C6	0.044 (3)	0.055 (3)	0.088 (5)	0.032 (3)	0.001 (4)	0.016 (4)
S3	0.0317 (7)	0.0351 (7)	0.0863 (12)	0.0160 (6)	−0.0036 (7)	−0.0017 (7)
O5	0.045 (2)	0.029 (2)	0.139 (4)	0.0071 (19)	−0.003 (3)	−0.001 (3)
O6	0.036 (2)	0.0323 (19)	0.110 (4)	0.0112 (17)	0.001 (2)	0.001 (2)
N5	0.029 (2)	0.041 (2)	0.084 (4)	0.016 (2)	0.004 (3)	−0.001 (3)
N6	0.036 (2)	0.034 (2)	0.078 (3)	0.0164 (19)	0.003 (3)	0.001 (2)
C7	0.036 (3)	0.037 (3)	0.067 (4)	0.014 (2)	0.003 (3)	−0.005 (3)
C8	0.033 (3)	0.032 (3)	0.064 (4)	0.012 (2)	0.003 (3)	−0.002 (3)
C9	0.059 (4)	0.027 (3)	0.127 (6)	0.016 (3)	0.009 (4)	0.004 (4)

Geometric parameters (Å, º) top

S1—C2	1.733 (5)	N3—N4	1.373 (5)
S1—C1	1.782 (5)	N3—H3D	0.8600
N1—C1	1.328 (6)	N4—C5	1.282 (6)
N1—N2	1.380 (5)	C6—H6A	0.9600
N1—H1A	0.8600	C6—H6B	0.9600
C1—O1	1.209 (6)	C6—H6C	0.9600
N2—C2	1.264 (6)	S3—C8	1.721 (5)
O2—C2	1.324 (6)	S3—C7	1.762 (6)
O2—C3	1.443 (7)	O5—C7	1.232 (6)
C3—H3A	0.9600	O6—C8	1.326 (6)
C3—H3B	0.9600	O6—C9	1.434 (7)
C3—H3C	0.9600	N5—C7	1.321 (6)
S2—C5	1.734 (5)	N5—N6	1.375 (6)
S2—C4	1.777 (5)	N5—H5A	0.8600
O3—C4	1.214 (5)	N6—C8	1.274 (6)
O4—C5	1.328 (5)	C9—H9A	0.9600
O4—C6	1.454 (6)	C9—H9B	0.9600
N3—C4	1.345 (6)	C9—H9C	0.9600

C2—S1—C1	88.1 (2)	N4—C5—O4	125.1 (4)
C1—N1—N2	120.3 (4)	N4—C5—S2	117.2 (4)
C1—N1—H1A	119.9	O4—C5—S2	117.7 (3)
N2—N1—H1A	119.9	O4—C6—H6A	109.5
O1—C1—N1	128.8 (5)	O4—C6—H6B	109.5
O1—C1—S1	125.1 (4)	H6A—C6—H6B	109.5
N1—C1—S1	106.1 (4)	O4—C6—H6C	109.5
C2—N2—N1	108.2 (4)	H6A—C6—H6C	109.5
C2—O2—C3	115.9 (4)	H6B—C6—H6C	109.5
N2—C2—O2	125.2 (4)	C8—S3—C7	87.5 (2)
N2—C2—S1	117.3 (4)	C8—O6—C9	116.3 (4)
O2—C2—S1	117.5 (4)	C7—N5—N6	118.7 (5)
O2—C3—H3A	109.5	C7—N5—H5A	120.7
O2—C3—H3B	109.5	N6—N5—H5A	120.7
H3A—C3—H3B	109.5	C8—N6—N5	108.2 (4)
O2—C3—H3C	109.5	O5—C7—N5	126.5 (5)
H3A—C3—H3C	109.5	O5—C7—S3	125.4 (4)
H3B—C3—H3C	109.5	N5—C7—S3	108.1 (4)
C5—S2—C4	88.1 (2)	N6—C8—O6	124.6 (4)
C5—O4—C6	114.7 (4)	N6—C8—S3	117.5 (4)
C4—N3—N4	119.6 (4)	O6—C8—S3	117.8 (3)
C4—N3—H3D	120.2	O6—C9—H9A	109.5
N4—N3—H3D	120.2	O6—C9—H9B	109.5
C5—N4—N3	108.3 (4)	H9A—C9—H9B	109.5
O3—C4—N3	127.9 (5)	O6—C9—H9C	109.5
O3—C4—S2	125.4 (4)	H9A—C9—H9C	109.5
N3—C4—S2	106.7 (3)	H9B—C9—H9C	109.5

N2—N1—C1—O1	−175.3 (7)	N3—N4—C5—S2	0.5 (7)
N2—N1—C1—S1	1.7 (7)	C6—O4—C5—N4	4.0 (10)
C2—S1—C1—O1	176.1 (6)	C6—O4—C5—S2	−175.8 (5)
C2—S1—C1—N1	−1.0 (5)	C4—S2—C5—N4	−1.8 (5)
C1—N1—N2—C2	−1.5 (8)	C4—S2—C5—O4	178.0 (5)
N1—N2—C2—O2	179.6 (6)	C7—N5—N6—C8	0.2 (9)
N1—N2—C2—S1	0.5 (8)	N6—N5—C7—O5	179.6 (7)
C3—O2—C2—N2	−5.2 (10)	N6—N5—C7—S3	−0.8 (7)
C3—O2—C2—S1	174.0 (5)	C8—S3—C7—O5	−179.5 (7)
C1—S1—C2—N2	0.3 (6)	C8—S3—C7—N5	0.9 (5)
C1—S1—C2—O2	−178.9 (5)	N5—N6—C8—O6	−179.9 (6)
C4—N3—N4—C5	1.7 (8)	N5—N6—C8—S3	0.6 (8)
N4—N3—C4—O3	177.5 (7)	C9—O6—C8—N6	3.4 (11)
N4—N3—C4—S2	−2.9 (7)	C9—O6—C8—S3	−177.1 (6)
C5—S2—C4—O3	−178.0 (6)	C7—S3—C8—N6	−0.9 (6)
C5—S2—C4—N3	2.4 (5)	C7—S3—C8—O6	179.6 (6)
N3—N4—C5—O4	−179.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.86	1.97	2.796 (7)	160
N3—H3D···O5	0.86	1.96	2.788 (6)	161
N5—H5A···O1ⁱⁱ	0.86	1.99	2.813 (8)	161

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

Experimental details

Crystal data
Chemical formula	C₃H₄N₂O₂S
M_r	132.16
Crystal system, space group	Hexagonal, P6₁
Temperature (K)	293
a, c (Å)	11.9240 (17), 20.111 (4)
V (Å³)	2476.3 (7)
Z	18
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.867, 0.909
No. of measured, independent and observed [I > 2σ(I)] reflections	3492, 3040, 2206
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.133, 1.04
No. of reflections	3040
No. of parameters	217
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.38
Absolute structure	Flack (1983), 1468 Friedel pairs
Absolute structure parameter	−0.05 (14)

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.8600	1.9700	2.796 (7)	160.00
N3—H3D···O5	0.8600	1.9600	2.788 (6)	161.00
N5—H5A···O1ⁱⁱ	0.8600	1.9900	2.813 (8)	161.00

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

Acknowledgements

This work was supported by the Doctoral Research Fund of Henan Chinese Medicine (BSJJ2009–42). The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

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