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

Abstract

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,

• a = 7.837 (3) Å

• b = 15.971 (5) Å

• c = 6.694 (2) Å

• β = 103.680 (4)°

• V = 814.1 (5) ų

• 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[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All the H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Figures

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).

Crystal data

C7H5N3S2	F(000) = 400
Mr = 195.26	Dx = 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

Rigaku Saturn CCD diffractometer	1928 independent reflections
Radiation source: fine-focus sealed tube	1642 reflections with I > 2σ(I)
graphite	Rint = 0.033
Detector resolution: 14.63 pixels mm-1	θmax = 27.8°, θmin = 2.6°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −20→21
Tmin = 0.891, Tmax = 0.954	l = −8→8
8141 measured reflections

Refinement

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(Fo2) + (0.0461P)2] where P = (Fo2 + 2Fc2)/3
1928 reflections	(Δ/σ)max < 0.001
113 parameters	Δρmax = 0.44 e Å−3
1 restraint	Δρmin = −0.21 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x, y−1/2, −z+1/2.