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Acta Cryst. (2008). E64, o1792    [ doi:10.1107/S1600536808026123 ]

4-(4-Amino-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)pyridinium chloride

X.-Y. Ren and F.-F. Jian

Abstract top

The crystal structure of the title compound, C7H8N5S+·Cl-, is stabilized by intermolecular N-H...Cl and N-H...S hydrogen-bond interactions.

Comment top

An important type of fungicides, triazole compounds are highly efficient and of low tocicity (Shi et al.,1995; Xu, et al., 2002). The part of our research is to find triazole with higher cooperational activity, we synthesized the title compound (I) and report its crystal structure here.

In the crystal structure of compound (I) (Fig. 1), the dihedral angle formed by the triazole ring (N1/N3/N4/C6/C7) and the pyridine ring (N1/C1-C5) was 0.7 (4)°. The C═S bond length [1.676 (3) Å] is in agreement with that observed before (Jian, et al., 2006). There are intermolecular N–H···Cl and N—H···S hydrogen-bond interactions to stabilize the crystal structure (Table 1).

Related literature top

For related literature, see: Jian et al. (2006); Shi et al. (1995); Xu et al. (2002).

Experimental top

The title compound (I) was prepared by the process as following: ethyl isonicotinate 1.51 g (0.01 mol) and hydrazine hydrate 0.32 g (0.01 mol) with ethanol at 377 K for 3 h, afford ivory-white compound A 1.32 g (yield 96%), then add 0.06 ml carbon disulfide and KOH 0.56 g (0.01 mol) with ethanol, stirred at room temperature for 5 h, afford yellow compound B 2.0 g (yield 85.6%). At last, add 0.32 g hydrazine hydrate to the compound B with water at 377 K for 12 h. Single crystals suitable for X-ray measurements were obtained by recrystallization from DMF-HCl (3:1) at 334 K.

Refinement top

The H atoms of the NH2 group were found from a difference Fourier map and refined freely. The other H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H and C—H distances of 0.86 and 0.93 Å, respectively, and with Uiso(H) = 1.2Ueq of the parent atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
4-(4-Amino-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)pyridinium chloride top
Crystal data top
C7H8N5S+·Cl–F000 = 472
Mr = 229.69Dx = 1.542 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.6740 (15) Åθ = 4–14º
b = 13.374 (3) ŵ = 0.56 mm−1
c = 9.965 (2) ÅT = 293 (2) K
β = 104.70 (3)ºBar, yellow
V = 989.3 (4) Å30.20 × 0.15 × 0.11 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.050
Radiation source: fine-focus sealed tubeθmax = 27.0º
Monochromator: graphiteθmin = 2.6º
T = 293(2) Kh = 0→9
ω scansk = 0→15
Absorption correction: nonel = −11→11
2238 measured reflections3 standard reflections
2091 independent reflections every 100 reflections
1712 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.111  w = 1/[σ2(Fo2) + (0.0626P)2 + 0.6426P]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
2091 reflectionsΔρmax = 0.35 e Å−3
135 parametersΔρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C7H8N5S+·Cl–V = 989.3 (4) Å3
Mr = 229.69Z = 4
Monoclinic, P21/cMo Kα
a = 7.6740 (15) ŵ = 0.56 mm−1
b = 13.374 (3) ÅT = 293 (2) K
c = 9.965 (2) Å0.20 × 0.15 × 0.11 mm
β = 104.70 (3)º
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.050
Absorption correction: none3 standard reflections
2238 measured reflections every 100 reflections
2091 independent reflections intensity decay: none
1712 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.038135 parameters
wR(F2) = 0.111H atoms treated by a mixture of
independent and constrained refinement
S = 0.96Δρmax = 0.35 e Å−3
2091 reflectionsΔρmin = −0.29 e Å−3
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
Cl10.80625 (8)0.86963 (4)0.12228 (5)0.04585 (18)
S10.75196 (9)0.94026 (5)0.52007 (7)0.0565 (2)
N10.0222 (2)0.78167 (16)−0.16338 (19)0.0469 (5)
H1A−0.05770.7735−0.24050.056*
N20.4905 (2)0.89786 (14)0.28259 (18)0.0376 (4)
N30.5917 (2)0.76955 (15)0.40203 (19)0.0452 (5)
H3A0.65050.73150.46760.054*
N40.4694 (3)0.73433 (15)0.28792 (19)0.0439 (4)
N50.4688 (4)0.99550 (16)0.2289 (3)0.0540 (6)
C10.0851 (3)0.7017 (2)−0.0868 (2)0.0494 (6)
H1B0.04300.6383−0.11730.059*
C20.2114 (3)0.71260 (18)0.0365 (2)0.0459 (5)
H2A0.25510.65680.09030.055*
C30.2744 (3)0.80777 (17)0.0811 (2)0.0362 (5)
C40.2062 (3)0.88900 (18)−0.0017 (2)0.0441 (5)
H4B0.24620.95330.02540.053*
C50.0786 (3)0.87364 (19)−0.1248 (2)0.0491 (6)
H5C0.03180.9278−0.18100.059*
C60.4102 (3)0.81438 (16)0.2152 (2)0.0367 (5)
C70.6114 (3)0.86845 (18)0.4025 (2)0.0402 (5)
H5A0.575 (5)1.011 (3)0.211 (4)0.092 (12)*
H5B0.443 (4)1.032 (2)0.290 (3)0.065 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0495 (3)0.0475 (3)0.0356 (3)0.0015 (2)0.0015 (2)0.0021 (2)
S10.0499 (4)0.0593 (4)0.0497 (4)−0.0019 (3)−0.0071 (3)−0.0162 (3)
N10.0392 (10)0.0627 (13)0.0340 (10)−0.0050 (9)0.0007 (7)−0.0061 (9)
N20.0357 (9)0.0395 (9)0.0353 (9)−0.0011 (7)0.0044 (7)−0.0037 (7)
N30.0436 (10)0.0493 (11)0.0356 (9)−0.0030 (9)−0.0030 (8)0.0022 (8)
N40.0440 (10)0.0465 (11)0.0354 (9)−0.0058 (8)−0.0004 (8)−0.0004 (8)
N50.0633 (15)0.0395 (12)0.0503 (13)0.0003 (10)−0.0024 (11)−0.0020 (10)
C10.0500 (13)0.0506 (14)0.0445 (12)−0.0123 (11)0.0063 (10)−0.0096 (11)
C20.0486 (12)0.0445 (13)0.0402 (12)−0.0047 (10)0.0035 (9)0.0002 (10)
C30.0324 (10)0.0451 (12)0.0317 (10)−0.0027 (9)0.0090 (8)−0.0032 (9)
C40.0464 (12)0.0421 (12)0.0397 (11)−0.0016 (10)0.0034 (9)−0.0017 (9)
C50.0498 (13)0.0509 (14)0.0403 (12)0.0037 (11)0.0000 (10)0.0018 (10)
C60.0340 (10)0.0409 (11)0.0350 (10)−0.0026 (8)0.0081 (8)−0.0009 (8)
C70.0348 (10)0.0491 (13)0.0347 (11)−0.0002 (9)0.0055 (8)−0.0043 (9)
Geometric parameters (Å, °) top
S1—C71.679 (2)N5—H5A0.90 (4)
N1—C51.328 (3)N5—H5B0.84 (3)
N1—C11.331 (3)C1—C21.366 (3)
N1—H1A0.8600C1—H1B0.9300
N2—C61.366 (3)C2—C31.394 (3)
N2—C71.371 (3)C2—H2A0.9300
N2—N51.405 (3)C3—C41.385 (3)
N3—C71.331 (3)C3—C61.474 (3)
N3—N41.362 (3)C4—C51.376 (3)
N3—H3A0.8600C4—H4B0.9300
N4—C61.308 (3)C5—H5C0.9300
C5—N1—C1122.28 (19)C1—C2—H2A120.2
C5—N1—H1A118.9C3—C2—H2A120.2
C1—N1—H1A118.9C4—C3—C2118.6 (2)
C6—N2—C7108.35 (18)C4—C3—C6124.5 (2)
C6—N2—N5125.26 (18)C2—C3—C6116.9 (2)
C7—N2—N5125.94 (19)C5—C4—C3119.3 (2)
C7—N3—N4113.60 (18)C5—C4—H4B120.3
C7—N3—H3A123.2C3—C4—H4B120.3
N4—N3—H3A123.2N1—C5—C4120.1 (2)
C6—N4—N3104.37 (18)N1—C5—H5C119.9
N2—N5—H5A105 (2)C4—C5—H5C119.9
N2—N5—H5B107 (2)N4—C6—N2110.29 (18)
H5A—N5—H5B114 (3)N4—C6—C3121.29 (19)
N1—C1—C2120.1 (2)N2—C6—C3128.43 (19)
N1—C1—H1B120.0N3—C7—N2103.35 (18)
C2—C1—H1B120.0N3—C7—S1128.55 (17)
C1—C2—C3119.6 (2)N2—C7—S1128.10 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.862.433.099 (2)135
N3—H3A···Cl1ii0.862.173.027 (2)176
N5—H5B···S1iii0.84 (3)2.72 (3)3.466 (3)148 (3)
Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.862.433.099 (2)135
N3—H3A···Cl1ii0.862.173.027 (2)176
N5—H5B···S1iii0.84 (3)2.72 (3)3.466 (3)148 (3)
Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+2, −z+1.
references
References top

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.

Jian, F.-F., Yu, H.-Q., Qiao, Y.-B. & Liang, T.-L. (2006). Acta Cryst. E62, o3416–o3417.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shi, Y. N., Lu, Y. C. & Fang, J. X. (1995). Chem. J. Chin. Univ. 16, 1710-1713.

Xu, L. Z., Zhang, S. S., Li, H. J. & Jiao, K. (2002). Chem. Res. Chin. Univ. 18, 284-286.