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

Ren, X.-Y.; Jian, F.-F.

doi:10.1107/S1600536808026123

organic compounds

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Volume 64| Part 9| September 2008| Page o1792

doi:10.1107/S1600536808026123

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

Xiao-Yan Ren ^a and Fang-Fang Jian ^a ^*

^aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 3 August 2008; accepted 13 August 2008; online 20 August 2008)

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

Related literature

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

Experimental

Crystal data

C₇H₈N₅S⁺·Cl⁻
M_r = 229.69
Monoclinic, P 2₁ /c
a = 7.6740 (15) Å
b = 13.374 (3) Å
c = 9.965 (2) Å
β = 104.70 (3)°
V = 989.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 293 (2) K
0.20 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2238 measured reflections
2091 independent reflections
1712 reflections with I > 2σ(I)
R_int = 0.050
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.111
S = 0.96
2091 reflections
135 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.86	2.43	3.099 (2)	135
N3—H3A⋯Cl1ⁱⁱ	0.86	2.17	3.027 (2)	176
N5—H5B⋯S1ⁱⁱⁱ	0.84 (3)	2.72 (3)	3.466 (3)	148 (3)
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+2, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026123/at2609sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808026123/at2609Isup2.hkl

checkCIF report

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.

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

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⁻	F(000) = 472
M_r = 229.69	D_x = 1.542 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.6740 (15) Å	θ = 4–14°
b = 13.374 (3) Å	µ = 0.56 mm⁻¹
c = 9.965 (2) Å	T = 293 K
β = 104.70 (3)°	Bar, yellow
V = 989.3 (4) Å³	0.20 × 0.15 × 0.11 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.050
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 2.6°
Graphite monochromator	h = 0→9
ω scans	k = 0→15
2238 measured reflections	l = −11→11
2091 independent reflections	3 standard reflections every 100 reflections
1712 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ²(F_o²) + (0.0626P)² + 0.6426P] where P = (F_o² + 2F_c²)/3
2091 reflections	(Δ/σ)_max < 0.001
135 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₈N₅S⁺·Cl⁻	V = 989.3 (4) Å³
M_r = 229.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6740 (15) Å	µ = 0.56 mm⁻¹
b = 13.374 (3) Å	T = 293 K
c = 9.965 (2) Å	0.20 × 0.15 × 0.11 mm
β = 104.70 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.050
2238 measured reflections	3 standard reflections every 100 reflections
2091 independent reflections	intensity decay: none
1712 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.35 e Å⁻³
2091 reflections	Δρ_min = −0.29 e Å⁻³
135 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
Cl1	0.80625 (8)	0.86963 (4)	0.12228 (5)	0.04585 (18)
S1	0.75196 (9)	0.94026 (5)	0.52007 (7)	0.0565 (2)
N1	0.0222 (2)	0.78167 (16)	−0.16338 (19)	0.0469 (5)
H1A	−0.0577	0.7735	−0.2405	0.056*
N2	0.4905 (2)	0.89786 (14)	0.28259 (18)	0.0376 (4)
N3	0.5917 (2)	0.76955 (15)	0.40203 (19)	0.0452 (5)
H3A	0.6505	0.7315	0.4676	0.054*
N4	0.4694 (3)	0.73433 (15)	0.28792 (19)	0.0439 (4)
N5	0.4688 (4)	0.99550 (16)	0.2289 (3)	0.0540 (6)
C1	0.0851 (3)	0.7017 (2)	−0.0868 (2)	0.0494 (6)
H1B	0.0430	0.6383	−0.1173	0.059*
C2	0.2114 (3)	0.71260 (18)	0.0365 (2)	0.0459 (5)
H2A	0.2551	0.6568	0.0903	0.055*
C3	0.2744 (3)	0.80777 (17)	0.0811 (2)	0.0362 (5)
C4	0.2062 (3)	0.88900 (18)	−0.0017 (2)	0.0441 (5)
H4B	0.2462	0.9533	0.0254	0.053*
C5	0.0786 (3)	0.87364 (19)	−0.1248 (2)	0.0491 (6)
H5C	0.0318	0.9278	−0.1810	0.059*
C6	0.4102 (3)	0.81438 (16)	0.2152 (2)	0.0367 (5)
C7	0.6114 (3)	0.86845 (18)	0.4025 (2)	0.0402 (5)
H5A	0.575 (5)	1.011 (3)	0.211 (4)	0.092 (12)*
H5B	0.443 (4)	1.032 (2)	0.290 (3)	0.065 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0495 (3)	0.0475 (3)	0.0356 (3)	0.0015 (2)	0.0015 (2)	0.0021 (2)
S1	0.0499 (4)	0.0593 (4)	0.0497 (4)	−0.0019 (3)	−0.0071 (3)	−0.0162 (3)
N1	0.0392 (10)	0.0627 (13)	0.0340 (10)	−0.0050 (9)	0.0007 (7)	−0.0061 (9)
N2	0.0357 (9)	0.0395 (9)	0.0353 (9)	−0.0011 (7)	0.0044 (7)	−0.0037 (7)
N3	0.0436 (10)	0.0493 (11)	0.0356 (9)	−0.0030 (9)	−0.0030 (8)	0.0022 (8)
N4	0.0440 (10)	0.0465 (11)	0.0354 (9)	−0.0058 (8)	−0.0004 (8)	−0.0004 (8)
N5	0.0633 (15)	0.0395 (12)	0.0503 (13)	0.0003 (10)	−0.0024 (11)	−0.0020 (10)
C1	0.0500 (13)	0.0506 (14)	0.0445 (12)	−0.0123 (11)	0.0063 (10)	−0.0096 (11)
C2	0.0486 (12)	0.0445 (13)	0.0402 (12)	−0.0047 (10)	0.0035 (9)	0.0002 (10)
C3	0.0324 (10)	0.0451 (12)	0.0317 (10)	−0.0027 (9)	0.0090 (8)	−0.0032 (9)
C4	0.0464 (12)	0.0421 (12)	0.0397 (11)	−0.0016 (10)	0.0034 (9)	−0.0017 (9)
C5	0.0498 (13)	0.0509 (14)	0.0403 (12)	0.0037 (11)	0.0000 (10)	0.0018 (10)
C6	0.0340 (10)	0.0409 (11)	0.0350 (10)	−0.0026 (8)	0.0081 (8)	−0.0009 (8)
C7	0.0348 (10)	0.0491 (13)	0.0347 (11)	−0.0002 (9)	0.0055 (8)	−0.0043 (9)

Geometric parameters (Å, º) top

S1—C7	1.679 (2)	N5—H5A	0.90 (4)
N1—C5	1.328 (3)	N5—H5B	0.84 (3)
N1—C1	1.331 (3)	C1—C2	1.366 (3)
N1—H1A	0.8600	C1—H1B	0.9300
N2—C6	1.366 (3)	C2—C3	1.394 (3)
N2—C7	1.371 (3)	C2—H2A	0.9300
N2—N5	1.405 (3)	C3—C4	1.385 (3)
N3—C7	1.331 (3)	C3—C6	1.474 (3)
N3—N4	1.362 (3)	C4—C5	1.376 (3)
N3—H3A	0.8600	C4—H4B	0.9300
N4—C6	1.308 (3)	C5—H5C	0.9300

C5—N1—C1	122.28 (19)	C1—C2—H2A	120.2
C5—N1—H1A	118.9	C3—C2—H2A	120.2
C1—N1—H1A	118.9	C4—C3—C2	118.6 (2)
C6—N2—C7	108.35 (18)	C4—C3—C6	124.5 (2)
C6—N2—N5	125.26 (18)	C2—C3—C6	116.9 (2)
C7—N2—N5	125.94 (19)	C5—C4—C3	119.3 (2)
C7—N3—N4	113.60 (18)	C5—C4—H4B	120.3
C7—N3—H3A	123.2	C3—C4—H4B	120.3
N4—N3—H3A	123.2	N1—C5—C4	120.1 (2)
C6—N4—N3	104.37 (18)	N1—C5—H5C	119.9
N2—N5—H5A	105 (2)	C4—C5—H5C	119.9
N2—N5—H5B	107 (2)	N4—C6—N2	110.29 (18)
H5A—N5—H5B	114 (3)	N4—C6—C3	121.29 (19)
N1—C1—C2	120.1 (2)	N2—C6—C3	128.43 (19)
N1—C1—H1B	120.0	N3—C7—N2	103.35 (18)
C2—C1—H1B	120.0	N3—C7—S1	128.55 (17)
C1—C2—C3	119.6 (2)	N2—C7—S1	128.10 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.43	3.099 (2)	135
N3—H3A···Cl1ⁱⁱ	0.86	2.17	3.027 (2)	176
N5—H5B···S1ⁱⁱⁱ	0.84 (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.

Experimental details

Crystal data
Chemical formula	C₇H₈N₅S⁺·Cl⁻
M_r	229.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.6740 (15), 13.374 (3), 9.965 (2)
β (°)	104.70 (3)
V (Å³)	989.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.20 × 0.15 × 0.11

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2238, 2091, 1712
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 0.96
No. of reflections	2091
No. of parameters	135
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.29

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.43	3.099 (2)	135.3
N3—H3A···Cl1ⁱⁱ	0.86	2.17	3.027 (2)	176.1
N5—H5B···S1ⁱⁱⁱ	0.84 (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

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jian, F.-F., Yu, H.-Q., Qiao, Y.-B. & Liang, T.-L. (2006). Acta Cryst. E62, o3416–o3417. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, Y. N., Lu, Y. C. & Fang, J. X. (1995). Chem. J. Chin. Univ. 16, 1710–1713. CAS Google Scholar
Xu, L. Z., Zhang, S. S., Li, H. J. & Jiao, K. (2002). Chem. Res. Chin. Univ. 18, 284–286. Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1792

doi:10.1107/S1600536808026123

Open

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