organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Xu, L. Z., Jiao, K., Zhang, S. S. & Kuang, S. P. (2002). Bull. Korean Chem. Soc. 23, 1699-1701.]); Jantova et al. (1998[Jantova, S., Greif, G., Paviovicova, R. & Cipak, L. (1998). Folia Microbiol. (Prague), 43, 75-80.]); Holla et al. (1996[Holla, B., Poojary, K., Kalluraya, B. & Gowda, P. (1996). Farmaco, 51, 793-799.]); Pevzner (1997[Pevzner, M. S. (1997). Russ. Khim. Zh. 41, 73-83.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C8H8N4S

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.736, Tmax = 0.939

  • 8689 measured reflections

  • 2134 independent reflections

  • 1464 reflections with I > 2σ(I)

  • Rint = 0.062

Refinement
  • R[F2 > 2σ(F2)] = 0.067

  • wR(F2) = 0.223

  • S = 1.12

  • 2134 reflections

  • 118 parameters

  • H-atom parameters constrained

  • Δρmax = 0.46 e Å−3

  • Δρmin = −0.44 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

All H atoms were initially located in a difference Fourier map, then they were constrained to ride on their parant atoms with C—H = 0.93 Å, N—H = 0.86-0.89 Å and with Uiso(H) = 1.2 Ueq(C, N).

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
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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
C8H8N4SF(000) = 400
Mr = 192.25Dx = 1.418 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1686 reflections
a = 5.5574 (4) Åθ = 3.2–27.5°
b = 25.2384 (3) ŵ = 0.31 mm1
c = 6.6327 (4) ÅT = 293 K
β = 104.511 (1)°Block, colourless
V = 900.63 (9) Å30.2 × 0.2 × 0.2 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer
2134 independent reflections
Radiation source: fine-focus sealed tube1464 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
Detector resolution: 13.6612 pixels mm-1θmax = 27.9°, θmin = 3.2°
CCD_Profile_fitting scansh = 77
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 3332
Tmin = 0.736, Tmax = 0.939l = 88
8689 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.223H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.1186P)2]
where P = (Fo2 + 2Fc2)/3
2134 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
C8H8N4SV = 900.63 (9) Å3
Mr = 192.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.5574 (4) ŵ = 0.31 mm1
b = 25.2384 (3) ÅT = 293 K
c = 6.6327 (4) Å0.2 × 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)
Tmin = 0.736, Tmax = 0.939Rint = 0.062
8689 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.223H-atom parameters constrained
S = 1.12Δρmax = 0.46 e Å3
2134 reflectionsΔρmin = 0.44 e Å3
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
xyzUiso*/Ueq
S10.12788 (16)0.01977 (3)0.82762 (13)0.0565 (3)
N30.4947 (5)0.08640 (10)0.7790 (4)0.0427 (6)
N20.3057 (5)0.05034 (10)0.4961 (4)0.0461 (6)
H2A0.20490.03110.40580.055*
N10.4798 (5)0.08322 (10)0.4454 (4)0.0478 (7)
C10.7971 (6)0.14417 (11)0.6429 (5)0.0413 (7)
C70.5948 (5)0.10520 (11)0.6248 (4)0.0405 (7)
C60.9052 (6)0.14961 (12)0.4763 (5)0.0465 (7)
H6A0.84890.12880.35810.056*
C80.3071 (6)0.05098 (11)0.6963 (5)0.0431 (7)
N40.5695 (6)0.09940 (12)0.9922 (4)0.0611 (8)
H4B0.62030.07021.06590.092*
H4D0.44090.11331.03120.092*
C51.0959 (6)0.18563 (13)0.4843 (6)0.0531 (8)
H5A1.16680.18890.37190.064*
C41.1802 (7)0.21651 (13)0.6595 (6)0.0566 (9)
H4C1.30880.24050.66580.068*
C20.8828 (8)0.17585 (14)0.8169 (6)0.0625 (10)
H2B0.81240.17320.92980.075*
C31.0756 (8)0.21171 (16)0.8214 (6)0.0703 (11)
H3A1.13300.23280.93870.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0563 (6)0.0662 (6)0.0481 (5)0.0193 (4)0.0153 (4)0.0046 (4)
N30.0450 (14)0.0473 (13)0.0346 (12)0.0077 (11)0.0079 (10)0.0004 (10)
N20.0478 (15)0.0508 (14)0.0406 (14)0.0148 (11)0.0126 (11)0.0067 (11)
N10.0475 (15)0.0538 (15)0.0440 (14)0.0102 (12)0.0153 (12)0.0050 (11)
C10.0407 (15)0.0386 (14)0.0446 (16)0.0013 (11)0.0105 (12)0.0017 (11)
C70.0432 (15)0.0408 (14)0.0389 (15)0.0019 (12)0.0128 (12)0.0005 (11)
C60.0465 (17)0.0545 (17)0.0396 (15)0.0057 (13)0.0130 (14)0.0005 (12)
C80.0436 (17)0.0434 (15)0.0414 (16)0.0051 (12)0.0086 (13)0.0015 (12)
N40.079 (2)0.0703 (18)0.0332 (14)0.0228 (16)0.0128 (13)0.0022 (13)
C50.0485 (18)0.0603 (19)0.0535 (19)0.0055 (15)0.0185 (15)0.0091 (15)
C40.0497 (18)0.0535 (19)0.068 (2)0.0110 (15)0.0168 (17)0.0027 (16)
C20.069 (2)0.071 (2)0.055 (2)0.0244 (18)0.0276 (17)0.0158 (17)
C30.077 (3)0.072 (2)0.067 (2)0.031 (2)0.027 (2)0.0212 (19)
Geometric parameters (Å, º) top
S1—C81.675 (3)C6—C51.387 (4)
N3—C71.366 (4)C6—H6A0.9300
N3—C81.378 (4)N4—H4B0.8900
N3—N41.409 (3)N4—H4D0.8900
N2—C81.326 (4)C5—C41.380 (5)
N2—N11.379 (3)C5—H5A0.9300
N2—H2A0.8600C4—C31.349 (5)
N1—C71.323 (4)C4—H4C0.9300
C1—C21.387 (4)C2—C31.397 (5)
C1—C61.390 (4)C2—H2B0.9300
C1—C71.476 (4)C3—H3A0.9300
C7—N3—C8109.7 (2)N2—C8—S1131.3 (2)
C7—N3—N4126.7 (2)N3—C8—S1125.9 (2)
C8—N3—N4123.6 (3)N3—N4—H4B109.3
C8—N2—N1114.1 (2)N3—N4—H4D109.1
C8—N2—H2A123.0H4B—N4—H4D109.5
N1—N2—H2A123.0C4—C5—C6119.8 (3)
C7—N1—N2104.1 (2)C4—C5—H5A120.1
C2—C1—C6118.5 (3)C6—C5—H5A120.1
C2—C1—C7123.2 (3)C3—C4—C5119.8 (3)
C6—C1—C7118.3 (3)C3—C4—H4C120.1
N1—C7—N3109.4 (2)C5—C4—H4C120.1
N1—C7—C1122.6 (3)C1—C2—C3119.6 (3)
N3—C7—C1128.0 (3)C1—C2—H2B120.2
C5—C6—C1120.8 (3)C3—C2—H2B120.2
C5—C6—H6A119.6C4—C3—C2121.5 (3)
C1—C6—H6A119.6C4—C3—H3A119.3
N2—C8—N3102.8 (2)C2—C3—H3A119.3
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···S1i0.862.463.310 (3)172
N4—H4B···S1ii0.892.673.506 (3)157
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+2.

Experimental details

Crystal data
Chemical formulaC8H8N4S
Mr192.25
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)5.5574 (4), 25.2384 (3), 6.6327 (4)
β (°) 104.511 (1)
V3)900.63 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.2 × 0.2 × 0.2
Data collection
DiffractometerRigaku Mercury2
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.736, 0.939
No. of measured, independent and
observed [I > 2σ(I)] reflections
8689, 2134, 1464
Rint0.062
(sin θ/λ)max1)0.657
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.223, 1.12
No. of reflections2134
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···S1i0.862.463.310 (3)171.9
N4—H4B···S1ii0.892.673.506 (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

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationHolla, B., Poojary, K., Kalluraya, B. & Gowda, P. (1996). Farmaco, 51, 793–799.  CAS PubMed Web of Science Google Scholar
First citationJantova, S., Greif, G., Paviovicova, R. & Cipak, L. (1998). Folia Microbiol. (Prague), 43, 75–80.  Web of Science CrossRef CAS Google Scholar
First citationPevzner, M. S. (1997). Russ. Khim. Zh. 41, 73–83.  CAS Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationXu, L. Z., Jiao, K., Zhang, S. S. & Kuang, S. P. (2002). Bull. Korean Chem. Soc. 23, 1699–1701.  CAS Google Scholar

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ISSN: 2056-9890
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