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

Zhao, Y.-Y.; Xing, Z.; Dai, W.; Han, G.-F.

doi:10.1107/S1600536808014967

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1169

doi:10.1107/S1600536808014967

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

Yu-Yuan Zhao,^a Zheng Xing,^a Wei Dai ^a and Guang-Fan Han ^a ^*

^aSchool of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, People's Republic of China
^*Correspondence e-mail: gf552002@yahoo.com.cn

(Received 24 April 2008; accepted 17 May 2008; online 30 May 2008)

In the title compound, C₈H₈N₄S, the planar triazole ring forms a dihedral angle of 13.7 (2)° with the phenyl ring. The crystal structure is stabilized by intermolecular N—H⋯S hydrogen-bond interactions, linking the molecules into chains along the a axis.

Related literature

For the applications of triazole compounds, see: Xu et al. (2002 ); Jantova et al. (1998 ); Holla et al. (1996 ); Pevzner (1997 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₈N₄S
M_r = 192.25
Monoclinic, P 2₁ /n
a = 5.5574 (4) Å
b = 25.2384 (3) Å
c = 6.6327 (4) Å
β = 104.511 (1)°
V = 900.63 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 (2) K
0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.736, T_max = 0.939
8689 measured reflections
2134 independent reflections
1464 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.223
S = 1.12
2134 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.86	2.46	3.310 (3)	172
N4—H4B⋯S1ⁱⁱ	0.89	2.67	3.506 (3)	157
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z+2.

Data collection: CrystalClear (Rigaku, 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/S1600536808014967/rz2214sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014967/rz2214Isup2.hkl

checkCIF report

Comment top

1,2,4-Triazole and its derivatives display a broad range of biological activities, finding application as antitumour, antibacterial, antifungal and antiviral agents (Xu et al., 2002; Jantova et al., 1998; Holla et al., 1996). Nitro derivatives of 1,2,4-triazole are also of interest as highly energetic compounds (Pevzner, 1997). In addition, studies have been carried out on the electronic structures and the thiol–thione tautomeric equilibrium of heterocyclic thione derivatives. In the search for compounds with better biological activity, the title compound was synthesized and we report its crystal structure here.

In the title compound (Fig. 1), the C—S bond length of 1.675 (3) Å is in good agreement with the mean value of 1.660 Å reported by Allen et al. (1987). The triazole ring is strictly planar and makes a dihedral angle of 13.7 (2)° with the phenyl ring. The crystal packing (Fig. 2) of is stabilized by intermolecular N—H···S hydrogen bonds (Table 1) linking the molecules into chains along the a axis.

Related literature top

For the applications of triazole compounds, see: Xu et al. (2002); Jantova et al. (1998); Holla et al. (1996); Pevzner (1997). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of KOH (0.015 mol, 0.840 g) and ethyl benzoate (0.01 mol, 1.50 g) in absolute ethanol (100 ml) was added CS₂ (0.015 mol, 0.91 ml). The mixture was diluted with absolute ethanol (50 ml) and shaken for 12 h. A suspension of the potassium salt, 98% hydrazine hydrate (0.03 mol, 15 ml) and absolute ethanol (10 ml) was refluxed with stirring for 4 h. Dilution with cold water (100 ml) and acidification with concentrated HCl precipitated a white solid. The product was then filtered and washed with cold water. Colourless crystals of the title compound suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of 100 mg in 15 ml diethylether after 3 days.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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 the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packing diagram of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₈H₈N₄S	F(000) = 400
M_r = 192.25	D_x = 1.418 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1686 reflections
a = 5.5574 (4) Å	θ = 3.2–27.5°
b = 25.2384 (3) Å	µ = 0.31 mm⁻¹
c = 6.6327 (4) Å	T = 293 K
β = 104.511 (1)°	Block, colourless
V = 900.63 (9) Å³	0.2 × 0.2 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	2134 independent reflections
Radiation source: fine-focus sealed tube	1464 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.9°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −33→32
T_min = 0.736, T_max = 0.939	l = −8→8
8689 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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.223	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.1186P)²] where P = (F_o² + 2F_c²)/3
2134 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₈H₈N₄S	V = 900.63 (9) Å³
M_r = 192.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.5574 (4) Å	µ = 0.31 mm⁻¹
b = 25.2384 (3) Å	T = 293 K
c = 6.6327 (4) Å	0.2 × 0.2 × 0.2 mm
β = 104.511 (1)°

Data collection top

Rigaku Mercury2 diffractometer	2134 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1464 reflections with I > 2σ(I)
T_min = 0.736, T_max = 0.939	R_int = 0.062
8689 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.223	H-atom parameters constrained
S = 1.12	Δρ_max = 0.46 e Å⁻³
2134 reflections	Δρ_min = −0.44 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	0.12788 (16)	0.01977 (3)	0.82762 (13)	0.0565 (3)
N3	0.4947 (5)	0.08640 (10)	0.7790 (4)	0.0427 (6)
N2	0.3057 (5)	0.05034 (10)	0.4961 (4)	0.0461 (6)
H2A	0.2049	0.0311	0.4058	0.055*
N1	0.4798 (5)	0.08322 (10)	0.4454 (4)	0.0478 (7)
C1	0.7971 (6)	0.14417 (11)	0.6429 (5)	0.0413 (7)
C7	0.5948 (5)	0.10520 (11)	0.6248 (4)	0.0405 (7)
C6	0.9052 (6)	0.14961 (12)	0.4763 (5)	0.0465 (7)
H6A	0.8489	0.1288	0.3581	0.056*
C8	0.3071 (6)	0.05098 (11)	0.6963 (5)	0.0431 (7)
N4	0.5695 (6)	0.09940 (12)	0.9922 (4)	0.0611 (8)
H4B	0.6203	0.0702	1.0659	0.092*
H4D	0.4409	0.1133	1.0312	0.092*
C5	1.0959 (6)	0.18563 (13)	0.4843 (6)	0.0531 (8)
H5A	1.1668	0.1889	0.3719	0.064*
C4	1.1802 (7)	0.21651 (13)	0.6595 (6)	0.0566 (9)
H4C	1.3088	0.2405	0.6658	0.068*
C2	0.8828 (8)	0.17585 (14)	0.8169 (6)	0.0625 (10)
H2B	0.8124	0.1732	0.9298	0.075*
C3	1.0756 (8)	0.21171 (16)	0.8214 (6)	0.0703 (11)
H3A	1.1330	0.2328	0.9387	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0563 (6)	0.0662 (6)	0.0481 (5)	−0.0193 (4)	0.0153 (4)	0.0046 (4)
N3	0.0450 (14)	0.0473 (13)	0.0346 (12)	−0.0077 (11)	0.0079 (10)	0.0004 (10)
N2	0.0478 (15)	0.0508 (14)	0.0406 (14)	−0.0148 (11)	0.0126 (11)	−0.0067 (11)
N1	0.0475 (15)	0.0538 (15)	0.0440 (14)	−0.0102 (12)	0.0153 (12)	−0.0050 (11)
C1	0.0407 (15)	0.0386 (14)	0.0446 (16)	−0.0013 (11)	0.0105 (12)	0.0017 (11)
C7	0.0432 (15)	0.0408 (14)	0.0389 (15)	−0.0019 (12)	0.0128 (12)	−0.0005 (11)
C6	0.0465 (17)	0.0545 (17)	0.0396 (15)	−0.0057 (13)	0.0130 (14)	0.0005 (12)
C8	0.0436 (17)	0.0434 (15)	0.0414 (16)	−0.0051 (12)	0.0086 (13)	0.0015 (12)
N4	0.079 (2)	0.0703 (18)	0.0332 (14)	−0.0228 (16)	0.0128 (13)	−0.0022 (13)
C5	0.0485 (18)	0.0603 (19)	0.0535 (19)	−0.0055 (15)	0.0185 (15)	0.0091 (15)
C4	0.0497 (18)	0.0535 (19)	0.068 (2)	−0.0110 (15)	0.0168 (17)	0.0027 (16)
C2	0.069 (2)	0.071 (2)	0.055 (2)	−0.0244 (18)	0.0276 (17)	−0.0158 (17)
C3	0.077 (3)	0.072 (2)	0.067 (2)	−0.031 (2)	0.027 (2)	−0.0212 (19)

Geometric parameters (Å, º) top

S1—C8	1.675 (3)	C6—C5	1.387 (4)
N3—C7	1.366 (4)	C6—H6A	0.9300
N3—C8	1.378 (4)	N4—H4B	0.8900
N3—N4	1.409 (3)	N4—H4D	0.8900
N2—C8	1.326 (4)	C5—C4	1.380 (5)
N2—N1	1.379 (3)	C5—H5A	0.9300
N2—H2A	0.8600	C4—C3	1.349 (5)
N1—C7	1.323 (4)	C4—H4C	0.9300
C1—C2	1.387 (4)	C2—C3	1.397 (5)
C1—C6	1.390 (4)	C2—H2B	0.9300
C1—C7	1.476 (4)	C3—H3A	0.9300

C7—N3—C8	109.7 (2)	N2—C8—S1	131.3 (2)
C7—N3—N4	126.7 (2)	N3—C8—S1	125.9 (2)
C8—N3—N4	123.6 (3)	N3—N4—H4B	109.3
C8—N2—N1	114.1 (2)	N3—N4—H4D	109.1
C8—N2—H2A	123.0	H4B—N4—H4D	109.5
N1—N2—H2A	123.0	C4—C5—C6	119.8 (3)
C7—N1—N2	104.1 (2)	C4—C5—H5A	120.1
C2—C1—C6	118.5 (3)	C6—C5—H5A	120.1
C2—C1—C7	123.2 (3)	C3—C4—C5	119.8 (3)
C6—C1—C7	118.3 (3)	C3—C4—H4C	120.1
N1—C7—N3	109.4 (2)	C5—C4—H4C	120.1
N1—C7—C1	122.6 (3)	C1—C2—C3	119.6 (3)
N3—C7—C1	128.0 (3)	C1—C2—H2B	120.2
C5—C6—C1	120.8 (3)	C3—C2—H2B	120.2
C5—C6—H6A	119.6	C4—C3—C2	121.5 (3)
C1—C6—H6A	119.6	C4—C3—H3A	119.3
N2—C8—N3	102.8 (2)	C2—C3—H3A	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.46	3.310 (3)	172
N4—H4B···S1ⁱⁱ	0.89	2.67	3.506 (3)	157

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₄S
M_r	192.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.5574 (4), 25.2384 (3), 6.6327 (4)
β (°)	104.511 (1)
V (Å³)	900.63 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.736, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	8689, 2134, 1464
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.223, 1.12
No. of reflections	2134
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.44

Computer programs: CrystalClear (Rigaku, 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
N2—H2A···S1ⁱ	0.86	2.46	3.310 (3)	171.9
N4—H4B···S1ⁱⁱ	0.89	2.67	3.506 (3)	157.4

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

Acknowledgements

This project was supported by Jiangsu Education Department of China (No. 05KJB350031)

References

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