5-(3-Pyrid­yl)-1,3,4-thia­diazol-2-amine

Wang, Y.; Wan, R.; Han, F.; Wang, P.

doi:10.1107/S1600536809019564

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1447

doi:10.1107/S1600536809019564

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5-(3-Pyridyl)-1,3,4-thiadiazol-2-amine

Yao Wang,^a Rong Wan,^a ^* Feng Han ^a and Peng Wang ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 21 May 2009; accepted 22 May 2009; online 29 May 2009)

The title compound, C₇H₆N₄S, was synthesized by reacting pyridine-3-carboxylic acid and thiosemicarbazide. The dihedral angle between the planes of the thiadiazole and pyridine rings is 32.42 (14)°. In the crystal structure, intermolecular N—H⋯N interactions link the molecules into a three-dimensional network, forming R₂²(8) ring motifs. π–π contacts between thiadiazole rings [centroid–centroid distance = 3.666 (1) Å] may further stabilize the structure.

Related literature

For general background, see: Nakagawa et al. (1996 ); Wang et al. (1999 ). For a related structure, see: Wang et al. (2009 ). For bond-length data, see: Allen et al. (1987 ). For ring-motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₆N₄S
M_r = 178.22
Monoclinic, P 2₁ /c
a = 11.066 (2) Å
b = 7.2380 (14) Å
c = 11.271 (2) Å
β = 116.79 (3)°
V = 805.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 294 K
0.10 × 0.05 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.966, T_max = 0.983
1542 measured reflections
1464 independent reflections
1220 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.132
S = 1.01
1464 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N3ⁱ	0.86	2.13	2.959 (3)	163
N4—H4B⋯N2ⁱⁱ	0.86	2.16	3.006 (3)	168
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); 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: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019564/hk2699sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019564/hk2699Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, and are in accordance with the corresponding values in 5-(4-pyridyl)-1,3,4-thiadiazol-2-amine (Wang et al., 2009). Rings A (N1/C1–C5) and B (S/N2/N3/C6/C7) are, of course, planar, and they are oriented at a dihedral angle of 32.42 (14)°.

In the crystal structure, intermolecular N—H···N interactions (Table 1) link the molecules into a three-dimensional network forming R₂²(8) ring motifs (Bernstein et al., 1995) (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the thiadiazole rings, Cg2—Cg2ⁱ, [symmetry code: (i) 1 - x, -y, 1 - z, where Cg2 is centroid of the ring B (S/N2/N3/C6/C7)] may further stabilize the structure, with centroid–centroid distance of 3.666 (1) Å.

Related literature top

For general background, see: Nakagawa et al. (1996); Wang et al. (1999). For a related structure, see: Wang et al. (2009). For bond-length data, see: Allen et al. (1987). For ring-motifs, see: Bernstein et al. (1995).

Experimental top

For the preparation of the title compound, 3-pyridine carboxylic acid (2 mmol) and thiosemicarbazide (5 mmol) were mixed in a 25 ml flask, and kept in the oil bath at 363 K for 6 h. After cooling, the crude product precipitated and was filted. Crystals of suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids at the 50% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

5-(3-Pyridyl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₇H₆N₄S	F(000) = 368
M_r = 178.22	D_x = 1.469 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 550 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.066 (2) Å	Cell parameters from 25 reflections
b = 7.2380 (14) Å	θ = 9–12°
c = 11.271 (2) Å	µ = 0.35 mm⁻¹
β = 116.79 (3)°	T = 294 K
V = 805.9 (3) Å³	Block, colourless
Z = 4	0.10 × 0.05 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1220 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.966, T_max = 0.983	l = −13→12
1542 measured reflections	3 standard reflections every 120 min
1464 independent reflections	intensity decay: 1%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.098P)²] where P = (F_o² + 2F_c²)/3
1464 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₇H₆N₄S	V = 805.9 (3) Å³
M_r = 178.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.066 (2) Å	µ = 0.35 mm⁻¹
b = 7.2380 (14) Å	T = 294 K
c = 11.271 (2) Å	0.10 × 0.05 × 0.05 mm
β = 116.79 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1220 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.026
T_min = 0.966, T_max = 0.983	3 standard reflections every 120 min
1542 measured reflections	intensity decay: 1%
1464 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
1464 reflections	Δρ_min = −0.34 e Å⁻³
109 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
S	0.69244 (6)	0.09005 (8)	0.45516 (5)	0.0434 (3)
N1	0.9145 (3)	−0.2801 (4)	0.8931 (2)	0.0717 (7)
N2	0.63999 (19)	0.1376 (3)	0.65128 (17)	0.0421 (5)
N3	0.57605 (19)	0.2824 (3)	0.56552 (18)	0.0441 (5)
N4	0.5428 (3)	0.3989 (3)	0.3599 (2)	0.0595 (7)
H4A	0.4944	0.4890	0.3645	0.071*
H4B	0.5580	0.3880	0.2918	0.071*
C1	0.9215 (3)	−0.4300 (4)	0.8284 (3)	0.0634 (8)
H1B	0.9692	−0.5315	0.8782	0.076*
C2	0.8626 (3)	−0.4435 (4)	0.6931 (3)	0.0628 (8)
H2B	0.8714	−0.5509	0.6523	0.075*
C3	0.7896 (3)	−0.2946 (3)	0.6177 (3)	0.0547 (7)
H3B	0.7483	−0.3004	0.5253	0.066*
C4	0.7792 (2)	−0.1374 (3)	0.6817 (2)	0.0407 (5)
C5	0.8440 (3)	−0.1375 (4)	0.8191 (3)	0.0578 (7)
H5A	0.8380	−0.0315	0.8628	0.069*
C6	0.7037 (2)	0.0273 (3)	0.6091 (2)	0.0378 (5)
C7	0.5946 (2)	0.2753 (3)	0.4591 (2)	0.0407 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0559 (4)	0.0461 (4)	0.0383 (4)	0.0125 (2)	0.0303 (3)	0.0041 (2)
N1	0.0875 (17)	0.0765 (17)	0.0569 (14)	0.0339 (14)	0.0375 (13)	0.0256 (13)
N2	0.0544 (11)	0.0423 (11)	0.0395 (10)	0.0099 (9)	0.0298 (9)	0.0079 (8)
N3	0.0609 (12)	0.0421 (11)	0.0427 (11)	0.0143 (9)	0.0353 (9)	0.0107 (8)
N4	0.0877 (16)	0.0626 (15)	0.0468 (12)	0.0360 (12)	0.0467 (12)	0.0221 (10)
C1	0.0656 (17)	0.0579 (18)	0.078 (2)	0.0224 (13)	0.0426 (16)	0.0289 (14)
C2	0.0675 (17)	0.0420 (15)	0.088 (2)	0.0143 (12)	0.0426 (16)	0.0072 (13)
C3	0.0616 (16)	0.0471 (15)	0.0563 (15)	0.0085 (12)	0.0273 (13)	0.0009 (12)
C4	0.0430 (12)	0.0419 (13)	0.0456 (13)	0.0048 (10)	0.0275 (10)	0.0068 (10)
C5	0.0728 (17)	0.0574 (16)	0.0491 (14)	0.0208 (13)	0.0327 (13)	0.0100 (12)
C6	0.0428 (12)	0.0396 (12)	0.0367 (11)	0.0026 (9)	0.0229 (10)	0.0034 (9)
C7	0.0505 (12)	0.0425 (12)	0.0359 (11)	0.0087 (10)	0.0256 (10)	0.0030 (9)

Geometric parameters (Å, º) top

S—C6	1.743 (2)	C1—C2	1.366 (4)
S—C7	1.736 (2)	C1—H1B	0.9300
N1—C1	1.329 (4)	C2—C3	1.385 (4)
N1—C5	1.335 (3)	C2—H2B	0.9300
N2—N3	1.384 (2)	C3—C4	1.379 (3)
N2—C6	1.289 (3)	C3—H3B	0.9300
N3—C7	1.306 (3)	C4—C5	1.383 (3)
N4—C7	1.342 (3)	C4—C6	1.474 (3)
N4—H4A	0.8600	C5—H5A	0.9300
N4—H4B	0.8600

C7—S—C6	86.65 (10)	C4—C3—H3B	120.5
C1—N1—C5	116.8 (3)	C2—C3—H3B	120.5
C6—N2—N3	113.79 (18)	C3—C4—C5	117.5 (2)
C7—N3—N2	111.67 (17)	C3—C4—C6	122.5 (2)
C7—N4—H4A	120.0	C5—C4—C6	120.0 (2)
C7—N4—H4B	120.0	N1—C5—C4	124.1 (3)
H4A—N4—H4B	120.0	N1—C5—H5A	117.9
N1—C1—C2	123.7 (2)	C4—C5—H5A	117.9
N1—C1—H1B	118.2	N2—C6—C4	124.3 (2)
C2—C1—H1B	118.2	N2—C6—S	113.59 (17)
C1—C2—C3	118.8 (3)	C4—C6—S	122.13 (16)
C1—C2—H2B	120.6	N3—C7—N4	123.6 (2)
C3—C2—H2B	120.6	N3—C7—S	114.30 (16)
C4—C3—C2	119.0 (3)	N4—C7—S	122.07 (16)

C5—N1—C1—C2	0.9 (5)	C3—C4—C6—N2	147.8 (2)
N1—C1—C2—C3	−0.9 (5)	C5—C4—C6—N2	−32.8 (3)
C6—N2—N3—C7	0.0 (3)	C3—C4—C6—S	−32.0 (3)
C1—C2—C3—C4	0.2 (4)	C5—C4—C6—S	147.4 (2)
C2—C3—C4—C5	0.5 (4)	C7—S—C6—N2	−0.09 (18)
C2—C3—C4—C6	179.9 (2)	C7—S—C6—C4	179.73 (19)
C1—N1—C5—C4	−0.1 (5)	N2—N3—C7—N4	179.7 (2)
C3—C4—C5—N1	−0.6 (4)	N2—N3—C7—S	−0.1 (3)
C6—C4—C5—N1	180.0 (3)	C6—S—C7—N3	0.10 (19)
N3—N2—C6—C4	−179.8 (2)	C6—S—C7—N4	−179.7 (2)
N3—N2—C6—S	0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3ⁱ	0.86	2.13	2.959 (3)	163
N4—H4B···N2ⁱⁱ	0.86	2.16	3.006 (3)	168

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

Experimental details

Crystal data
Chemical formula	C₇H₆N₄S
M_r	178.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	11.066 (2), 7.2380 (14), 11.271 (2)
β (°)	116.79 (3)
V (Å³)	805.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.966, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	1542, 1464, 1220
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.132, 1.01
No. of reflections	1464
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.34

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3ⁱ	0.86	2.13	2.959 (3)	163
N4—H4B···N2ⁱⁱ	0.86	2.16	3.006 (3)	168

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

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

References

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