4-Amino-3-(4-pyrid­yl)-1,2,4-triazole-5(4H)-thione

Zou, F.; Xuan, W.-M.; Fang, X.-M.; Zhang, H.

doi:10.1107/S1600536807064331

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o213

https://doi.org/10.1107/S1600536807064331

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4-Amino-3-(4-pyridyl)-1,2,4-triazole-5(4H)-thione

Fang Zou,^a Wei-Min Xuan,^a Xue-Ming Fang ^a and Hui Zhang ^a ^*

^aState Key Laboratory for the Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: tristanzou@yahoo.com.cn

(Received 13 November 2007; accepted 29 November 2007; online 6 December 2007)

In the title molecule, C₇H₇N₅S, the pyridyl and triazole rings form a dihedral angle of 20.07 (6)°. Intermolecular N—H⋯N hydrogen bonds link the molecules into chains extended in the direction [10 $[\overline 1]$ ]. Further stability is provided by π⋯π stacking interactions, indicated by short distances between the centroids of triazole rings [3.480 (5) Å] and pyridyl rings [3.574 (5) Å] of neighbouring molecules.

Related literature

For the biological activities of related compounds, see: Eweiss et al. (1986 ); Awad et al. (1991 ). For a similar structure, see Kajdan et al. (2000 ).

Experimental

Crystal data

C₇H₇N₅S
M_r = 193.24
Monoclinic, C 2/c
a = 7.722 (6) Å
b = 14.215 (11) Å
c = 15.068 (12) Å
β = 93.432 (15)°
V = 1651 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 273 (2) K
0.15 × 0.10 × 0.08 mm

Data collection

Bruker APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.950, T_max = 0.973
4402 measured reflections
1626 independent reflections
1116 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.169
S = 1.01
1626 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯N1ⁱ	0.86	1.91	2.772 (4)	175
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and ViewerPro (Accelrys, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064331/cv2366sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064331/cv2366Isup2.hkl

checkCIF report

Comment top

Amine- and thione-substituted triazoles have been studied as anti-inflammatory and antimicrobial agents (Eweiss et al., 1986; Awad et al., 1991). Herein, we report the structure of the title compound, (I).

In (I) (Fig. 1), the molecule exists as a thione tautomer. All bond lengths and angles are normal and comparable with those found in related compounds (Kajdan et al., 2000). The dihedral angle between the pyridinyl and triazole rings is 20.07 (6)°.

In the crystal, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into chains extending in direction [10–1]. Further stability is provided by π···π stacking interactions supported by short distances between the centroids of pyridine (Cg1) and triazole (Cg2) rings, respectively - Cg1···Cg1ⁱⁱ 3.574 (5) Å, Cg2···Cg2ⁱⁱⁱ 3.480 (5) Å [symmetry codes: (ii) 1/2 - x, 3/2 - y, -z; (iii) -x, y, 1/2 - z].

Related literature top

For the biological activities of related compounds, see: Eweiss et al. (1986); Awad et al. (1991). For a similar structure, see Kajdan et al. (2000).

Experimental top

Potassium hydroxide (8.4 g, 0.15 mol) in 100 ml of absolute ethanol was added to isonicotinohydrazide (13.7 g, 0.10 mol) under ice bath. The mixture was stirred until the solution became clear, and carbon disulfide (9.04 ml, 0.15 mol) was added. The solution was reacted for 12 h at room temperature and 100 ml dried ethyl ether were added to form a precipitate, which was filtered and washed with ethyl ether several times. The precipitate was mixed with hydrazine hydrate (8.0 g, 160 mmol) and 10 ml water. The solution was refluxed for 2 h until the colour of the solution became clear green. After cooling to room temperature, 100 ml ice water was added and neutralized with 3M hydrochloric acid to form the precipitate, which was isolated by filtration and purified by recrystallization from ethanol to give pure 3-pyridinyl-4-amino-5- -mercapto-1,2,4-triazole. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of an Dimethylformamide solution.

Structure description top

For the biological activities of related compounds, see: Eweiss et al. (1986); Awad et al. (1991). For a similar structure, see Kajdan et al. (2000).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1997) and ViewerPro (Accelrys, 2001); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids.

4-Amino-3-(4-pyridyl)-1,2,4-triazole-5(4H)-thione top

Crystal data top

C₇H₇N₅S	F(000) = 800
M_r = 193.24	D_x = 1.555 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.722 (6) Å	Cell parameters from 1061 reflections
b = 14.215 (11) Å	θ = 2.7–23.8°
c = 15.068 (12) Å	µ = 0.35 mm⁻¹
β = 93.432 (15)°	T = 273 K
V = 1651 (2) Å³	Clubbed, colourless
Z = 8	0.15 × 0.10 × 0.08 mm

Data collection top

Bruker APEX area-detector diffractometer	1626 independent reflections
Radiation source: fine-focus sealed tube	1116 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
φ and ω scan	θ_max = 26.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.950, T_max = 0.973	k = −16→17
4402 measured reflections	l = −8→18

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0857P)² + 0.3739P] where P = (F_o² + 2F_c²)/3
1626 reflections	(Δ/σ)_max = 0.048
118 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₇H₇N₅S	V = 1651 (2) Å³
M_r = 193.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 7.722 (6) Å	µ = 0.35 mm⁻¹
b = 14.215 (11) Å	T = 273 K
c = 15.068 (12) Å	0.15 × 0.10 × 0.08 mm
β = 93.432 (15)°

Data collection top

Bruker APEX area-detector diffractometer	1626 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1116 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.973	R_int = 0.060
4402 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
1626 reflections	Δρ_min = −0.28 e Å⁻³
118 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	0.11589 (13)	0.51429 (7)	0.38748 (7)	0.0572 (4)
N5	0.2341 (3)	0.73058 (19)	0.24951 (19)	0.0425 (8)
C6	0.2889 (4)	0.6629 (2)	0.2010 (2)	0.0362 (8)
N3	0.2571 (3)	0.57925 (19)	0.2400 (2)	0.0414 (7)
C3	0.3732 (4)	0.6799 (2)	0.1189 (2)	0.0366 (8)
N1	0.5323 (3)	0.7249 (2)	−0.0353 (2)	0.0468 (8)
N4	0.1676 (3)	0.68743 (19)	0.31970 (19)	0.0401 (7)
H4B	0.1229	0.7172	0.3624	0.048*
C7	0.1781 (4)	0.5945 (2)	0.3160 (2)	0.0409 (9)
C1	0.5178 (5)	0.7863 (3)	0.0293 (3)	0.0551 (11)
H1A	0.5630	0.8462	0.0219	0.066*
N2	0.2980 (4)	0.49002 (19)	0.2082 (2)	0.0579 (10)
H2B	0.2642	0.4458	0.2463	0.087*
H2C	0.2407	0.4820	0.1550	0.087*
C4	0.3874 (5)	0.6154 (3)	0.0534 (3)	0.0564 (11)
H4A	0.3438	0.5550	0.0596	0.068*
C5	0.4670 (5)	0.6408 (3)	−0.0219 (3)	0.0591 (11)
H5A	0.4753	0.5959	−0.0663	0.071*
C2	0.4414 (4)	0.7675 (3)	0.1055 (2)	0.0493 (10)
H2A	0.4350	0.8138	0.1488	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0686 (7)	0.0505 (6)	0.0540 (7)	0.0022 (5)	0.0170 (6)	0.0140 (5)
N5	0.0460 (16)	0.0430 (16)	0.0394 (18)	−0.0043 (12)	0.0104 (15)	−0.0002 (13)
C6	0.0297 (16)	0.0445 (19)	0.034 (2)	−0.0018 (13)	0.0000 (15)	0.0030 (16)
N3	0.0415 (15)	0.0405 (16)	0.0433 (18)	0.0031 (11)	0.0118 (14)	0.0008 (13)
C3	0.0259 (15)	0.0485 (19)	0.035 (2)	0.0043 (13)	0.0030 (15)	0.0050 (16)
N1	0.0402 (15)	0.062 (2)	0.0383 (19)	0.0031 (14)	0.0070 (14)	0.0012 (16)
N4	0.0420 (15)	0.0470 (17)	0.0324 (17)	−0.0008 (12)	0.0111 (14)	0.0011 (13)
C7	0.0330 (16)	0.043 (2)	0.047 (2)	0.0027 (14)	0.0053 (17)	0.0025 (16)
C1	0.064 (2)	0.048 (2)	0.055 (3)	−0.0077 (17)	0.018 (2)	0.002 (2)
N2	0.076 (2)	0.0413 (17)	0.060 (2)	0.0057 (15)	0.0273 (19)	−0.0025 (16)
C4	0.070 (2)	0.047 (2)	0.053 (3)	−0.0123 (18)	0.018 (2)	−0.005 (2)
C5	0.077 (3)	0.059 (3)	0.043 (2)	−0.002 (2)	0.021 (2)	−0.0063 (19)
C2	0.061 (2)	0.046 (2)	0.042 (2)	0.0017 (17)	0.0151 (19)	−0.0012 (17)

Geometric parameters (Å, º) top

S1—C7	1.659 (4)	N4—C7	1.325 (4)
N5—C6	1.295 (4)	N4—H4B	0.8600
N5—N4	1.350 (4)	C1—C2	1.349 (5)
C6—N3	1.356 (4)	C1—H1A	0.9300
C6—C3	1.452 (4)	N2—H2B	0.9000
N3—C7	1.347 (4)	N2—H2C	0.8999
N3—N2	1.399 (4)	C4—C5	1.371 (5)
C3—C4	1.355 (5)	C4—H4A	0.9300
C3—C2	1.372 (5)	C5—H5A	0.9300
N1—C5	1.319 (5)	C2—H2A	0.9300
N1—C1	1.317 (5)

C6—N5—N4	104.9 (3)	N3—C7—S1	127.2 (3)
N5—C6—N3	109.5 (3)	N1—C1—C2	124.0 (3)
N5—C6—C3	122.4 (3)	N1—C1—H1A	118.0
N3—C6—C3	128.1 (3)	C2—C1—H1A	118.0
C7—N3—C6	109.3 (3)	N3—N2—H2B	109.6
C7—N3—N2	124.1 (3)	N3—N2—H2C	108.1
C6—N3—N2	126.6 (3)	H2B—N2—H2C	109.5
C4—C3—C2	117.3 (3)	C3—C4—C5	119.0 (4)
C4—C3—C6	124.6 (3)	C3—C4—H4A	120.5
C2—C3—C6	118.1 (3)	C5—C4—H4A	120.5
C5—N1—C1	115.9 (3)	N1—C5—C4	124.1 (4)
C7—N4—N5	113.1 (3)	N1—C5—H5A	118.0
C7—N4—H4B	123.4	C4—C5—H5A	118.0
N5—N4—H4B	123.4	C1—C2—C3	119.7 (3)
N4—C7—N3	103.2 (3)	C1—C2—H2A	120.1
N4—C7—S1	129.6 (3)	C3—C2—H2A	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N1ⁱ	0.86	1.91	2.772 (4)	175

Symmetry code: (i) x−1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₇N₅S
M_r	193.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	7.722 (6), 14.215 (11), 15.068 (12)
β (°)	93.432 (15)
V (Å³)	1651 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.15 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.950, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	4402, 1626, 1116
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.169, 1.01
No. of reflections	1626
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.28

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Farrugia, 1997) and ViewerPro (Accelrys, 2001), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N1ⁱ	0.86	1.91	2.772 (4)	174.8

Symmetry code: (i) x−1/2, −y+3/2, z+1/2.

Acknowledgements

The authors thank the Provincial NSF of Fujian Province of China (grant No. 2005YZ1020) and the NSF of Xiamen University (Series B, grant No. XDKJCX20061027).

References

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