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

Liu, X.-F.; Liu, X.-H.

doi:10.1107/S1600536810052116

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o202

https://doi.org/10.1107/S1600536810052116

Open

access

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

Xu-Feng Liu ^a and Xing-Hai Liu ^b ^*

^aDepartment of Chemical Engineering, Ningbo University of Technology, Ningbo 315016, People's Republic of China, and ^bCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: xhliu@zjut.edu.cn

(Received 11 December 2010; accepted 12 December 2010; online 18 December 2010)

The title compound C₇H₅N₃S₂, occurs as the thione tautomer in the solid state; the dihedral angle between the pyridine and thiadiazole ring planes is 2.08 (6)°. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, generating C(8) chains propagating in [010].

Related literature

For details of the synthesis, see: Song et al. (2005 ). For the biological activity of related compounds, see: Liu et al. (2007 , 2009a ,b ,c ).

Experimental

Crystal data

C₇H₅N₃S₂
M_r = 195.26
Monoclinic, P 2₁ /c
a = 7.837 (3) Å
b = 15.971 (5) Å
c = 6.694 (2) Å
β = 103.680 (4)°
V = 814.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 113 K
0.20 × 0.20 × 0.08 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.891, T_max = 0.954
8141 measured reflections
1928 independent reflections
1642 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.076
S = 1.06
1928 reflections
113 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.90 (1)	1.85 (1)	2.7395 (19)	169 (2)
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810052116/hb5770sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052116/hb5770Isup2.hkl

checkCIF report

Comment top

Thidiazoles had excellent biological activities, such as fungicide, KARI (Liu et al., 2007, 2009a,b,c). Meanwhile, some nicotine structure are also exhibited good biological activity. In continuated our work, a thidiazoles derivatives had been synthesized. The strucuture was confirmed by X-ray crstallography.

Single-crystal X-ray diffraction analysis reveals that the title compound crystallizes in the monoclinic space group P2(1)/c. As shown in Fig. 1, the pyridine ring and the thiadiazole ring are nearly in the same plane [dihedral angle = 2.1 °]. As shown in Fig. 2, the crystal structure is stabilized by weak N—H···N intermolecular interactions.

Related literature top

For details of the synthesis, see: Song et al. (2005). For the biological activity of related compounds, see: Liu et al. (2007, 2009a,b,c).

Experimental top

Potassium hydroxide (0.11 mol) was dissolved in minimum amount of ethanol, and 4-nicotinehydrazide (0.1 mol) was added to it. The reaction mixture was cooled to 0–5 °C followed by dropwise addition of carbon disulfide (0.11 mol). After addition, the reaction mixture was stirred for 30 min to afford solid potassium dithiocarbazate salt. It was filtered, washed with EtOH, dried, and used as such for further reaction. Potassium dithiocarbazate salt (0.1 mol) was added slowly in small lots to conc sulfuric acid (2.5 times of salt) at 5 °C with constant stirring. The reaction mixture was stirred for 30 min, and the resulting viscous liquid was poured over crushed ice slowly. The solid obtained was filtered and washed and dried to get the title compound. The compound was recrystallized in DMF to yield colorless prisms.

Structure description top

For details of the synthesis, see: Song et al. (2005). For the biological activity of related compounds, see: Liu et al. (2007, 2009a,b,c).

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing for (I).

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

Crystal data top

C₇H₅N₃S₂	F(000) = 400
M_r = 195.26	D_x = 1.593 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2887 reflections
a = 7.837 (3) Å	θ = 2.6–27.9°
b = 15.971 (5) Å	µ = 0.59 mm⁻¹
c = 6.694 (2) Å	T = 113 K
β = 103.680 (4)°	Prism, colorless
V = 814.1 (5) Å³	0.20 × 0.20 × 0.08 mm
Z = 4

Data collection top

Rigaku Saturn CCD diffractometer	1928 independent reflections
Radiation source: fine-focus sealed tube	1642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.8°, θ_min = 2.6°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −20→21
T_min = 0.891, T_max = 0.954	l = −8→8
8141 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0461P)²] where P = (F_o² + 2F_c²)/3
1928 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.44 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₇H₅N₃S₂	V = 814.1 (5) Å³
M_r = 195.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.837 (3) Å	µ = 0.59 mm⁻¹
b = 15.971 (5) Å	T = 113 K
c = 6.694 (2) Å	0.20 × 0.20 × 0.08 mm
β = 103.680 (4)°

Data collection top

Rigaku Saturn CCD diffractometer	1928 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1642 reflections with I > 2σ(I)
T_min = 0.891, T_max = 0.954	R_int = 0.033
8141 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	1 restraint
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.44 e Å⁻³
1928 reflections	Δρ_min = −0.21 e Å⁻³
113 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	0.40446 (4)	0.02171 (2)	0.20702 (6)	0.01704 (11)
S2	0.60139 (5)	−0.14291 (2)	0.26909 (6)	0.02389 (13)
N1	0.27180 (16)	−0.11033 (7)	0.30185 (19)	0.0159 (3)
N2	0.13949 (15)	−0.05360 (7)	0.28751 (18)	0.0151 (2)
N3	−0.14570 (15)	0.23252 (7)	0.15350 (18)	0.0154 (3)
C1	0.42543 (17)	−0.08492 (8)	0.2646 (2)	0.0159 (3)
C2	0.19024 (17)	0.01952 (8)	0.2396 (2)	0.0138 (3)
C3	0.07477 (17)	0.09310 (8)	0.2109 (2)	0.0138 (3)
C4	0.13479 (18)	0.17060 (8)	0.1615 (2)	0.0160 (3)
H4	0.2515	0.1772	0.1463	0.019*
C5	0.02020 (18)	0.23800 (8)	0.1349 (2)	0.0159 (3)
H5	0.0617	0.2909	0.1018	0.019*
C6	−0.20252 (18)	0.15758 (8)	0.2012 (2)	0.0156 (3)
H6	−0.3202	0.1529	0.2145	0.019*
C7	−0.09795 (17)	0.08668 (9)	0.2320 (2)	0.0156 (3)
H7	−0.1426	0.0348	0.2667	0.019*
H1	0.244 (3)	−0.1638 (6)	0.325 (3)	0.047 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01417 (18)	0.01237 (18)	0.0254 (2)	−0.00003 (12)	0.00638 (15)	0.00162 (13)
S2	0.0190 (2)	0.0213 (2)	0.0318 (3)	0.00798 (14)	0.00682 (17)	0.00402 (15)
N1	0.0171 (6)	0.0109 (5)	0.0204 (7)	0.0014 (4)	0.0058 (5)	0.0016 (5)
N2	0.0171 (6)	0.0117 (5)	0.0170 (6)	0.0013 (5)	0.0048 (5)	0.0001 (4)
N3	0.0164 (6)	0.0132 (6)	0.0158 (6)	−0.0001 (5)	0.0021 (5)	−0.0016 (4)
C1	0.0169 (7)	0.0139 (6)	0.0162 (7)	0.0003 (5)	0.0025 (5)	−0.0005 (5)
C2	0.0142 (6)	0.0137 (6)	0.0137 (7)	−0.0005 (5)	0.0039 (5)	−0.0014 (5)
C3	0.0160 (7)	0.0136 (6)	0.0115 (7)	0.0002 (5)	0.0026 (5)	−0.0014 (5)
C4	0.0146 (7)	0.0158 (7)	0.0179 (7)	−0.0014 (5)	0.0046 (6)	−0.0002 (5)
C5	0.0183 (7)	0.0123 (6)	0.0167 (7)	−0.0022 (5)	0.0037 (6)	0.0000 (5)
C6	0.0142 (6)	0.0170 (7)	0.0158 (7)	−0.0015 (5)	0.0040 (6)	−0.0017 (5)
C7	0.0177 (7)	0.0126 (7)	0.0164 (7)	−0.0025 (5)	0.0042 (6)	−0.0006 (5)

Geometric parameters (Å, º) top

S1—C2	1.7437 (15)	C2—C3	1.4679 (18)
S1—C1	1.7452 (15)	C3—C4	1.3916 (19)
S2—C1	1.6555 (14)	C3—C7	1.3974 (18)
N1—C1	1.3485 (18)	C4—C5	1.3862 (19)
N1—N2	1.3631 (16)	C4—H4	0.9500
N1—H1	0.902 (9)	C5—H5	0.9500
N2—C2	1.2980 (17)	C6—C7	1.3844 (19)
N3—C5	1.3378 (18)	C6—H6	0.9500
N3—C6	1.3417 (17)	C7—H7	0.9500

C2—S1—C1	89.77 (6)	C7—C3—C2	120.65 (12)
C1—N1—N2	118.98 (11)	C5—C4—C3	118.43 (13)
C1—N1—H1	125.1 (12)	C5—C4—H4	120.8
N2—N1—H1	115.7 (13)	C3—C4—H4	120.8
C2—N2—N1	110.06 (11)	N3—C5—C4	123.48 (12)
C5—N3—C6	117.71 (11)	N3—C5—H5	118.3
N1—C1—S2	127.20 (11)	C4—C5—H5	118.3
N1—C1—S1	107.03 (10)	N3—C6—C7	123.17 (13)
S2—C1—S1	125.77 (8)	N3—C6—H6	118.4
N2—C2—C3	122.50 (12)	C7—C6—H6	118.4
N2—C2—S1	114.16 (10)	C6—C7—C3	118.57 (12)
C3—C2—S1	123.33 (10)	C6—C7—H7	120.7
C4—C3—C7	118.64 (12)	C3—C7—H7	120.7
C4—C3—C2	120.71 (12)

C1—N1—N2—C2	−0.77 (17)	N2—C2—C3—C7	−0.8 (2)
N2—N1—C1—S2	−178.87 (10)	S1—C2—C3—C7	177.65 (11)
N2—N1—C1—S1	0.50 (15)	C7—C3—C4—C5	−0.1 (2)
C2—S1—C1—N1	−0.08 (10)	C2—C3—C4—C5	179.66 (12)
C2—S1—C1—S2	179.29 (11)	C6—N3—C5—C4	0.3 (2)
N1—N2—C2—C3	179.24 (12)	C3—C4—C5—N3	−0.3 (2)
N1—N2—C2—S1	0.65 (15)	C5—N3—C6—C7	0.1 (2)
C1—S1—C2—N2	−0.34 (11)	N3—C6—C7—C3	−0.5 (2)
C1—S1—C2—C3	−178.92 (12)	C4—C3—C7—C6	0.5 (2)
N2—C2—C3—C4	179.40 (13)	C2—C3—C7—C6	−179.28 (12)
S1—C2—C3—C4	−2.14 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.90 (1)	1.85 (1)	2.7395 (19)	169 (2)

Symmetry code: (i) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₅N₃S₂
M_r	195.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	7.837 (3), 15.971 (5), 6.694 (2)
β (°)	103.680 (4)
V (Å³)	814.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.20 × 0.20 × 0.08

Data collection
Diffractometer	Rigaku Saturn CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.891, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	8141, 1928, 1642
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.076, 1.06
No. of reflections	1928
No. of parameters	113
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.21

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
N1—H1···N3ⁱ	0.904 (12)	1.846 (14)	2.7395 (19)	169 (2)

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (No. 21002090) and the Key Laboratory of Pesticide Chemistry and Applications, Ministry of Agriculture (MOA), Beijing, People's Republic of China (No. MOAPCA201005) and the Scientific Research Fund of Zhejiang Education Department (Y201018479).

References

Liu, X. H., Chen, P. Q., Wang, B. L., Li, Y. H., Wang, S. H. & Li, Z. M. (2007). Bioorg. Med. Chem. Lett. 17, 3784–3788. Web of Science CSD CrossRef PubMed CAS Google Scholar
Liu, X. H., Shi, Y. X., Ma, Y., He, G. R., Dong, W. L., Zhang, C. Y., Wang, B. L., Wang, S. H., Li, B. J. & Li, Z. M. (2009a). Chem. Biol. Drug Des. 73, 320–327. Web of Science CrossRef PubMed CAS Google Scholar
Liu, X. H., Shi, Y. X., Ma, Y., Zhang, C. Y., Dong, W. L., Li, P., Wang, B. L., Li, B. J. & Li, Z. M. (2009b). Eur. J. Med. Chem. 44, 2782–2786. Web of Science CrossRef PubMed CAS Google Scholar
Liu, X. H., Zhang, C. Y., Guo, W. C., Li, Y. H., Chen, P. Q., Wang, T., Dong, W. L., Sun, H. W. & Li, Z. M. (2009c). J. Enzym. Inhib. Med. Chem. 24, 545–552. Web of Science CrossRef CAS Google Scholar
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, B. A., Chen, C. J., Yang, S., Jin, L. H., Xue, W., Zhang, S. M., Zou, Z. H., Hu, D. Y. & Liu, G. (2005). Acta Chem. Sin. 18, 1720–1726. Google Scholar