N-(5-Methyl­sulfanyl-1,3,4-thia­diazol-2-yl)acetamide

Zhang, G.-Y.

doi:10.1107/S1600536809030554

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2138

doi:10.1107/S1600536809030554

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N-(5-Methylsulfanyl-1,3,4-thiadiazol-2-yl)acetamide

Guo-Ying Zhang ^a ^*

^aCollege of Chemistry and Life Science, Tianjin Normal University, Tianjin 300074, People's Republic of China
^*Correspondence e-mail: hsxyzgy@mail.tjnu.edu.cn

(Received 21 July 2009; accepted 31 July 2009; online 12 August 2009)

In the title compound, C₅H₇N₃OS₂, inversion dimers linked by pairs of N—H⋯N hydrogen bonds occur, forming R₂²(8) ring motifs. These dimers are arranged into chains via intermolecular C—H⋯O hydrogen bonds between the methylsulfanyl groups and the O atoms of the carbonyl groups. The acetamido-1,3,4-thiodiazole unit is essentially planar [r.m.s. deviation 0.045 (8) Å].

Related literature

For the applications of 1,3,4-thiodiazole and its derivatives in antimicrobial drugs and in the construction of metal-organic frameworks, see: Gardinier et al. (2007 ); Mrozek et al. (2000 ); Xue et al. (2008 ). For the synthesis, see: Clerici & Pocar (2001 ).

Experimental

Crystal data

C₅H₇N₃OS₂
M_r = 189.26
Triclinic, $[P \overline 1]$
a = 5.0797 (10) Å
b = 7.9894 (16) Å
c = 10.081 (2) Å
α = 91.96 (3)°
β = 90.94 (3)°
γ = 105.27 (3)°
V = 394.32 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.836, T_max = 0.941
3437 measured reflections
1382 independent reflections
1259 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.078
S = 1.07
1382 reflections
106 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N2ⁱ	0.77 (2)	2.12 (2)	2.881 (2)	173 (2)
C1—H1B⋯O1ⁱⁱ	0.96	2.58	3.289 (3)	131 (2)
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku/MSC, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536809030554/bq2155sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030554/bq2155Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiodiazole is important for biological systems, and its derivatives have attracted widespread interest due to their further expanded application in antimicrobial drugs and in the construction of some interesting metal-organic frameworks (Gardinier et al., 2007; Mrozek et al., 2000; Xue et al., 2008). Recently, we synthesized a new thiodiazole-ligand, namely 2-acetamido-5-methylmercapto-1,3,4-thiodiazole, (I). Herein we report the crystal structure of this ligand.

The molecular structure of (I) is shown in Fig. 1. The acetamido-1,3,4-thiodiazole moiety is essentially planar (r.m.s. deviation 0.045 (8) Å), forming a dihedral angle with the C1, S1 and C2 plane of atoms of 14.6 (9)°. In the crystal, inversion dimers linked by pairs of N—H···N hydrogen bonds occur, forming R₂²(8) ring motifs. These dimers are arranged into chains via intermolecular C—H···O hydrogen bonds between the methyl groups and the O atoms of the carbonyl groups (Fig. 2).

Related literature top

For the applications of 1,3,4-thiodiazole and its derivatives in antimicrobial drugs and in the construction of metal-organic frameworks, see: Gardinier et al. (2007); Mrozek et al. (2000); Xue et al. (2008). For the synthesis, see: Clerici et al. (2001).

Experimental top

The title compound was prepared according to the literature (Clerici et al., 2001). 5-Methylsulfanyl-1,3,4-thiadiazol-2-ylamine (3.239 g, 0.022 mol) was suspended in acetic anhydride (2.28 ml, 0.024 mol), and acetic acid (9 ml) was added under stirring. The reaction mixture was further stirred at 313 K for 20 min. After cooling, water (10 ml) was added to the mixture, and then the precipitate was recrystallized in EtOH, which gave single crystals suitable for X-ray diffraction analysis (yield: 3.331 g, 80%).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 30% probability level.
	Fig. 2. The chain structure linked by N—H···N (pink) and C—H···O (blue) hydrogen bonds in (I).

N-(5-Methylsulfanyl-1,3,4-thiadiazol-2-yl)acetamide top

Crystal data top

C₅H₇N₃OS₂	Z = 2
M_r = 189.26	F(000) = 196
Triclinic, P1	D_x = 1.594 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0797 (10) Å	Cell parameters from 3437 reflections
b = 7.9894 (16) Å	θ = 3.3–27.6°
c = 10.081 (2) Å	µ = 0.62 mm⁻¹
α = 91.96 (3)°	T = 293 K
β = 90.94 (3)°	Block, yellow
γ = 105.27 (3)°	0.30 × 0.30 × 0.10 mm
V = 394.32 (14) Å³

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1382 independent reflections
Radiation source: fine-focus sealed tube	1259 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −6→6
T_min = 0.836, T_max = 0.941	k = −9→9
3437 measured reflections	l = −11→11

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0418P)² + 0.1675P] where P = (F_o² + 2F_c²)/3
1382 reflections	(Δ/σ)_max = 0.001
106 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₅H₇N₃OS₂	γ = 105.27 (3)°
M_r = 189.26	V = 394.32 (14) Å³
Triclinic, P1	Z = 2
a = 5.0797 (10) Å	Mo Kα radiation
b = 7.9894 (16) Å	µ = 0.62 mm⁻¹
c = 10.081 (2) Å	T = 293 K
α = 91.96 (3)°	0.30 × 0.30 × 0.10 mm
β = 90.94 (3)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1382 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1259 reflections with I > 2σ(I)
T_min = 0.836, T_max = 0.941	R_int = 0.016
3437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.25 e Å⁻³
1382 reflections	Δρ_min = −0.24 e Å⁻³
106 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
C1	0.8654 (4)	0.6728 (3)	0.3920 (2)	0.0434 (5)
H1A	0.8055	0.5632	0.4333	0.065*
H1B	0.9004	0.6534	0.3002	0.065*
H1C	0.7261	0.7336	0.3984	0.065*
C2	1.0570 (4)	0.8285 (2)	0.63353 (18)	0.0267 (4)
C3	0.8380 (4)	0.8321 (2)	0.83774 (18)	0.0260 (4)
C4	0.4332 (4)	0.6973 (2)	0.95823 (19)	0.0282 (4)
C5	0.2992 (4)	0.7042 (3)	1.0889 (2)	0.0358 (5)
H5A	0.1062	0.6539	1.0780	0.054*
H5B	0.3327	0.8229	1.1205	0.054*
H5C	0.3730	0.6404	1.1521	0.054*
H3	0.732 (5)	0.878 (3)	1.008 (2)	0.039 (7)*
N1	1.2055 (3)	0.9415 (2)	0.71786 (16)	0.0324 (4)
N2	1.0764 (3)	0.9425 (2)	0.83800 (16)	0.0312 (4)
N3	0.6785 (3)	0.8170 (2)	0.94718 (17)	0.0300 (4)
O1	0.3383 (3)	0.59336 (19)	0.86769 (14)	0.0406 (4)
S1	1.17277 (10)	0.80015 (7)	0.47435 (5)	0.03824 (18)
S2	0.74395 (9)	0.71212 (6)	0.69103 (5)	0.02978 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0426 (13)	0.0547 (14)	0.0290 (11)	0.0073 (11)	−0.0009 (9)	−0.0095 (10)
C2	0.0247 (9)	0.0298 (10)	0.0247 (9)	0.0057 (7)	0.0016 (7)	0.0004 (7)
C3	0.0256 (10)	0.0268 (9)	0.0237 (10)	0.0041 (8)	0.0004 (7)	−0.0039 (7)
C4	0.0253 (10)	0.0280 (10)	0.0298 (10)	0.0046 (8)	0.0011 (8)	−0.0005 (8)
C5	0.0328 (11)	0.0379 (11)	0.0336 (11)	0.0036 (9)	0.0085 (9)	0.0009 (9)
N1	0.0286 (9)	0.0358 (9)	0.0290 (9)	0.0021 (7)	0.0051 (7)	−0.0041 (7)
N2	0.0264 (9)	0.0336 (9)	0.0279 (9)	−0.0012 (7)	0.0038 (7)	−0.0062 (7)
N3	0.0266 (9)	0.0327 (9)	0.0246 (9)	−0.0017 (7)	0.0023 (7)	−0.0087 (7)
O1	0.0339 (8)	0.0409 (8)	0.0369 (8)	−0.0064 (6)	0.0029 (6)	−0.0117 (7)
S1	0.0323 (3)	0.0532 (4)	0.0271 (3)	0.0080 (2)	0.0066 (2)	−0.0043 (2)
S2	0.0256 (3)	0.0336 (3)	0.0247 (3)	−0.0007 (2)	0.00124 (19)	−0.00701 (19)

Geometric parameters (Å, º) top

C1—S1	1.796 (2)	C3—S2	1.7244 (19)
C1—H1A	0.9600	C4—O1	1.216 (2)
C1—H1B	0.9600	C4—N3	1.365 (3)
C1—H1C	0.9600	C4—C5	1.499 (3)
C2—N1	1.294 (3)	C5—H5A	0.9600
C2—S2	1.737 (2)	C5—H5B	0.9600
C2—S1	1.7457 (19)	C5—H5C	0.9600
C3—N2	1.297 (2)	N1—N2	1.387 (2)
C3—N3	1.369 (3)	N3—H3	0.77 (2)

S1—C1—H1A	109.5	N3—C4—C5	114.83 (17)
S1—C1—H1B	109.5	C4—C5—H5A	109.5
H1A—C1—H1B	109.5	C4—C5—H5B	109.5
S1—C1—H1C	109.5	H5A—C5—H5B	109.5
H1A—C1—H1C	109.5	C4—C5—H5C	109.5
H1B—C1—H1C	109.5	H5A—C5—H5C	109.5
N1—C2—S2	115.25 (14)	H5B—C5—H5C	109.5
N1—C2—S1	120.67 (15)	C2—N1—N2	111.35 (16)
S2—C2—S1	124.08 (11)	C3—N2—N1	112.70 (15)
N2—C3—N3	120.95 (17)	C4—N3—C3	124.71 (17)
N2—C3—S2	114.78 (14)	C4—N3—H3	117.4 (18)
N3—C3—S2	124.27 (14)	C3—N3—H3	117.8 (18)
O1—C4—N3	121.00 (18)	C2—S1—C1	101.30 (10)
O1—C4—C5	124.16 (18)	C3—S2—C2	85.91 (9)

S2—C2—N1—N2	0.3 (2)	S2—C3—N3—C4	4.8 (3)
S1—C2—N1—N2	−179.74 (13)	N1—C2—S1—C1	−166.91 (17)
N3—C3—N2—N1	−178.87 (17)	S2—C2—S1—C1	13.04 (15)
S2—C3—N2—N1	0.6 (2)	N2—C3—S2—C2	−0.35 (15)
C2—N1—N2—C3	−0.6 (2)	N3—C3—S2—C2	179.09 (17)
O1—C4—N3—C3	−0.2 (3)	N1—C2—S2—C3	0.01 (16)
C5—C4—N3—C3	178.85 (18)	S1—C2—S2—C3	−179.95 (13)
N2—C3—N3—C4	−175.77 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2ⁱ	0.77 (2)	2.12 (2)	2.881 (2)	173 (2)
C1—H1B···O1ⁱⁱ	0.96	2.58	3.289 (3)	131 (2)

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₅H₇N₃OS₂
M_r	189.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.0797 (10), 7.9894 (16), 10.081 (2)
α, β, γ (°)	91.96 (3), 90.94 (3), 105.27 (3)
V (Å³)	394.32 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.836, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	3437, 1382, 1259
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.078, 1.07
No. of reflections	1382
No. of parameters	106
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.24

Computer programs: CrystalClear (Rigaku/MSC, 2005), 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
N3—H3···N2ⁱ	0.77 (2)	2.12 (2)	2.881 (2)	173 (2)
C1—H1B···O1ⁱⁱ	0.96	2.58	3.289 (3)	131 (2)

Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1.

Acknowledgements

We are grateful for financial support from the Program for Excellent Introduced Talents of Tianjin Normal University in China (No. 5RL052).

References

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