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

Zhao, G.-Q.; Pan, Z.-F.; Tang, X.-X.

doi:10.1107/S1600536807062848

organic compounds

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Volume 64| Part 1| January 2008| Page o138

https://doi.org/10.1107/S1600536807062848

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

Guang-Qiang Zhao,^a Zhi-Fang Pan ^b and Xue-Xi Tang ^a ^*

^aCollege of Marine Life Sciences, Ocean University of China, Qingdao 266003, People's Republic of China, and ^bWeifang Medical University, Weifang 261042, People's Republic of China
^*Correspondence e-mail: tangxx@ouc.edu.cn

(Received 22 November 2007; accepted 24 November 2007; online 6 December 2007)

In the title compound, C₇H₈N₅S⁺·Cl⁻, the dihedral angle formed by the pyridine ring with the triazole ring is 10.0 (1)°. There are weak intermolecular hydrogen-bond interactions in the crystal structure, involving the NH and NH₂ groups as donors, and the chloride anion, the S atom in the thioketone group and the unsubstituted ring N atom as acceptors.

Related literature

For related literature, see: Gilchrist (1998 ); Jian et al. (2007 ).

Experimental

Crystal data

C₇H₈N₅S⁺·Cl⁻
M_r = 229.69
Monoclinic, P 2₁ /c
a = 7.2290 (14) Å
b = 12.922 (3) Å
c = 11.253 (4) Å
β = 114.90 (2)°
V = 953.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 293 (2) K
0.20 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
6085 measured reflections
2301 independent reflections
2071 reflections with I > 2σ(I)
R_int = 0.017
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.089
S = 0.87
2301 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1	0.86	2.21	3.0715 (13)	175
N5—H5A⋯Cl1ⁱ	0.86	2.51	3.1740 (14)	135
N5—H5A⋯Cl1ⁱⁱ	0.86	2.55	3.1999 (15)	133
N1—H1A⋯S1ⁱⁱⁱ	0.87 (2)	2.74 (2)	3.5381 (19)	153.4 (18)
N1—H1B⋯Cl1^iv	0.88 (2)	2.51 (2)	3.300 (2)	149.5 (18)
N1—H1B⋯N4ⁱⁱ	0.88 (2)	2.69 (2)	3.1199 (19)	111.7 (16)
Symmetry codes: (i) $[x+1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iii) -x+1, -y-1, -z; (iv) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062848/at2512sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062848/at2512Isup2.hkl

checkCIF report

Comment top

Five- and six-membered heterocyclic compounds are important constituents that often exist in biologically active natural products and synthetic compounds of medicinal interest (Gilchrist,1998). The title compound (I), is known to coordinate metal centres in a variety of coordination modes involving all combination of the S and N atoms. So it was synthesized and we report here its crystal structure.

In the crystal structure of (I) (Fig. 1), the dihedral angle formed by the pyridine ring (C1—C5/N5) and the plane of the (N2—N4/C6/C7) ring was 10.0 (1)°. The C? S bond length of 1.666 (3)Å is in agreement with that observed before (Jian et al., 2007). In the crystal structure, there are N—H···S and N—H···N and N—H···Cl hydrogen-bond interactions to stabilize the molecular packing (table 2).

Related literature top

For related literature, see: Gilchrist (1998); Jian et al. (2007).

Experimental top

A mixture of nicotinic acid hydrazide (0.02 mol), carbon disulfide (0.02 mol) and potassium hydroxide (0.02 mol) was stirred with ethanol (50 ml) at 293 K for 5 h, the yellow precipitate was formed, upon collection by filtration,the deposit was washed with ethanol and dried for one day in air.Then dissolved in water (100 ml), hydrazine hydrate was added at 353 K with stirring.then afford the title compound (2.4 g, yield 62%). Single crystals suitable for X-ray measurements were obtained by recrystallization from 10% HCl liquor at room temperature.

Structure description top

For related literature, see: Gilchrist (1998); Jian et al. (2007).

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, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.

3-(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 = 1.600 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2290 (14) Å	Cell parameters from 25 reflections
b = 12.922 (3) Å	θ = 4–14°
c = 11.253 (4) Å	µ = 0.59 mm⁻¹
β = 114.90 (2)°	T = 293 K
V = 953.5 (4) Å³	Black, yellow
Z = 4	0.20 × 0.15 × 0.11 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.017
Radiation source: fine-focus sealed tube	θ_max = 28.3°, θ_min = 2.5°
Graphite monochromator	h = −6→9
ω scans	k = −17→16
6085 measured reflections	l = −14→14
2301 independent reflections	3 standard reflections every 100 reflections
2071 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0625P)² + 0.3755P] where P = (F_o² + 2F_c²)/3
S = 0.87	(Δ/σ)_max < 0.001
2301 reflections	Δρ_max = 0.33 e Å⁻³
140 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (2)

Crystal data top

C₇H₈N₅S⁺·Cl⁻	V = 953.5 (4) Å³
M_r = 229.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2290 (14) Å	µ = 0.59 mm⁻¹
b = 12.922 (3) Å	T = 293 K
c = 11.253 (4) Å	0.20 × 0.15 × 0.11 mm
β = 114.90 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.017
6085 measured reflections	3 standard reflections every 100 reflections
2301 independent reflections	intensity decay: none
2071 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	Δρ_max = 0.33 e Å⁻³
2301 reflections	Δρ_min = −0.25 e Å⁻³
140 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	0.21801 (6)	−0.06699 (3)	−0.00811 (4)	0.04580 (14)
S1	0.27272 (7)	−0.39138 (3)	−0.07565 (4)	0.04812 (14)
N1	0.5768 (2)	−0.45060 (10)	−0.20638 (17)	0.0452 (3)
N2	0.52602 (18)	−0.34784 (9)	−0.19273 (11)	0.0338 (3)
N3	0.41277 (19)	−0.21399 (9)	−0.13746 (12)	0.0389 (3)
H3A	0.3507	−0.1739	−0.1051	0.047*
N4	0.5307 (2)	−0.17818 (9)	−0.19636 (12)	0.0388 (3)
N5	0.9097 (2)	−0.33194 (10)	−0.40767 (12)	0.0410 (3)
H5A	0.9391	−0.3863	−0.4404	0.049*
C1	0.9917 (2)	−0.24258 (13)	−0.41851 (16)	0.0437 (3)
H1C	1.0785	−0.2393	−0.4603	0.052*
C2	0.9465 (3)	−0.15530 (13)	−0.36718 (18)	0.0497 (4)
H2A	1.0010	−0.0918	−0.3747	0.060*
C3	0.8196 (2)	−0.16212 (12)	−0.30438 (16)	0.0431 (3)
H3B	0.7896	−0.1032	−0.2685	0.052*
C4	0.7363 (2)	−0.25703 (10)	−0.29446 (13)	0.0332 (3)
C5	0.7842 (2)	−0.34241 (11)	−0.34905 (14)	0.0386 (3)
C6	0.5992 (2)	−0.26159 (10)	−0.22922 (13)	0.0326 (3)
C7	0.4025 (2)	−0.31668 (11)	−0.13467 (13)	0.0346 (3)
H5B	0.738 (3)	−0.4045 (15)	−0.3468 (18)	0.045 (5)*
H1A	0.569 (3)	−0.4851 (18)	−0.142 (2)	0.061 (6)*
H1B	0.476 (3)	−0.4713 (16)	−0.279 (2)	0.052 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0618 (3)	0.0326 (2)	0.0622 (3)	0.00315 (15)	0.0448 (2)	0.00064 (14)
S1	0.0556 (3)	0.0435 (2)	0.0606 (3)	0.00530 (16)	0.0394 (2)	0.00822 (16)
N1	0.0599 (8)	0.0267 (6)	0.0637 (9)	0.0062 (6)	0.0405 (8)	0.0028 (6)
N2	0.0410 (6)	0.0273 (5)	0.0391 (6)	0.0041 (4)	0.0227 (5)	−0.0006 (4)
N3	0.0475 (7)	0.0340 (6)	0.0448 (6)	0.0052 (5)	0.0289 (6)	−0.0025 (5)
N4	0.0492 (7)	0.0314 (6)	0.0448 (7)	0.0030 (5)	0.0285 (6)	−0.0026 (5)
N5	0.0513 (7)	0.0378 (6)	0.0430 (7)	0.0076 (5)	0.0288 (6)	−0.0008 (5)
C1	0.0441 (8)	0.0484 (8)	0.0478 (8)	0.0044 (6)	0.0284 (7)	0.0042 (6)
C2	0.0540 (9)	0.0391 (8)	0.0680 (10)	−0.0043 (7)	0.0372 (8)	0.0002 (7)
C3	0.0486 (8)	0.0328 (7)	0.0561 (9)	−0.0003 (6)	0.0300 (7)	−0.0056 (6)
C4	0.0365 (6)	0.0324 (6)	0.0334 (6)	0.0031 (5)	0.0173 (5)	−0.0008 (5)
C5	0.0513 (8)	0.0306 (7)	0.0423 (7)	0.0020 (6)	0.0280 (6)	−0.0007 (5)
C6	0.0382 (7)	0.0294 (6)	0.0329 (6)	0.0021 (5)	0.0176 (5)	−0.0016 (5)
C7	0.0379 (7)	0.0353 (7)	0.0342 (6)	0.0054 (5)	0.0185 (5)	0.0009 (5)

Geometric parameters (Å, º) top

S1—C7	1.6667 (15)	N5—C5	1.3339 (19)
N1—N2	1.4032 (16)	N5—H5A	0.8600
N1—H1A	0.87 (2)	C1—C2	1.368 (2)
N1—H1B	0.88 (2)	C1—H1C	0.9300
N2—C6	1.3686 (17)	C2—C3	1.376 (2)
N2—C7	1.3703 (17)	C2—H2A	0.9300
N3—C7	1.3302 (19)	C3—C4	1.391 (2)
N3—N4	1.3625 (17)	C3—H3B	0.9300
N3—H3A	0.8600	C4—C5	1.3762 (19)
N4—C6	1.3029 (17)	C4—C6	1.4622 (19)
N5—C1	1.327 (2)	C5—H5B	0.874 (19)

N2—N1—H1A	106.4 (15)	C1—C2—H2A	120.2
N2—N1—H1B	103.6 (14)	C3—C2—H2A	120.2
H1A—N1—H1B	107 (2)	C2—C3—C4	120.16 (14)
C6—N2—C7	108.38 (11)	C2—C3—H3B	119.9
C6—N2—N1	125.86 (12)	C4—C3—H3B	119.9
C7—N2—N1	125.69 (12)	C5—C4—C3	118.15 (13)
C7—N3—N4	113.76 (11)	C5—C4—C6	122.90 (13)
C7—N3—H3A	123.1	C3—C4—C6	118.94 (12)
N4—N3—H3A	123.1	N5—C5—C4	119.39 (14)
C6—N4—N3	104.32 (12)	N5—C5—H5B	117.2 (13)
C1—N5—C5	123.85 (13)	C4—C5—H5B	123.4 (13)
C1—N5—H5A	118.1	N4—C6—N2	110.35 (12)
C5—N5—H5A	118.1	N4—C6—C4	121.86 (12)
N5—C1—C2	118.87 (14)	N2—C6—C4	127.79 (12)
N5—C1—H1C	120.6	N3—C7—N2	103.17 (12)
C2—C1—H1C	120.6	N3—C7—S1	129.32 (11)
C1—C2—C3	119.57 (15)	N2—C7—S1	127.51 (11)

C7—N3—N4—C6	−1.15 (17)	C7—N2—C6—C4	180.00 (13)
C5—N5—C1—C2	−0.1 (2)	N1—N2—C6—C4	2.9 (2)
N5—C1—C2—C3	0.8 (3)	C5—C4—C6—N4	−169.13 (14)
C1—C2—C3—C4	−0.7 (3)	C3—C4—C6—N4	9.6 (2)
C2—C3—C4—C5	−0.1 (2)	C5—C4—C6—N2	11.6 (2)
C2—C3—C4—C6	−178.92 (15)	C3—C4—C6—N2	−169.64 (14)
C1—N5—C5—C4	−0.8 (2)	N4—N3—C7—N2	1.52 (16)
C3—C4—C5—N5	0.8 (2)	N4—N3—C7—S1	−178.52 (11)
C6—C4—C5—N5	179.58 (13)	C6—N2—C7—N3	−1.28 (15)
N3—N4—C6—N2	0.25 (15)	N1—N2—C7—N3	175.79 (14)
N3—N4—C6—C4	−179.13 (12)	C6—N2—C7—S1	178.76 (11)
C7—N2—C6—N4	0.67 (16)	N1—N2—C7—S1	−4.2 (2)
N1—N2—C6—N4	−176.40 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1	0.86	2.21	3.0715 (13)	175
N5—H5A···Cl1ⁱ	0.86	2.51	3.1740 (14)	135
N5—H5A···Cl1ⁱⁱ	0.86	2.55	3.1999 (15)	133
N1—H1A···S1ⁱⁱⁱ	0.87 (2)	2.74 (2)	3.5381 (19)	153.4 (18)
N1—H1B···Cl1^iv	0.88 (2)	2.51 (2)	3.300 (2)	149.5 (18)
N1—H1B···N4ⁱⁱ	0.88 (2)	2.69 (2)	3.1199 (19)	111.7 (16)

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

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)	7.2290 (14), 12.922 (3), 11.253 (4)
β (°)	114.90 (2)
V (Å³)	953.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
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	6085, 2301, 2071
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.089, 0.87
No. of reflections	2301
No. of parameters	140
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL/PC (Sheldrick, 1997b), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1	0.86	2.21	3.0715 (13)	174.9
N5—H5A···Cl1ⁱ	0.86	2.51	3.1740 (14)	134.5
N5—H5A···Cl1ⁱⁱ	0.86	2.55	3.1999 (15)	132.6
N1—H1A···S1ⁱⁱⁱ	0.87 (2)	2.74 (2)	3.5381 (19)	153.4 (18)
N1—H1B···Cl1^iv	0.88 (2)	2.51 (2)	3.300 (2)	149.5 (18)
N1—H1B···N4ⁱⁱ	0.88 (2)	2.69 (2)	3.1199 (19)	111.7 (16)

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

References

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. 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
Gilchrist, T. L. (1998). Heterocyclic Chemistry, 3rd ed. London: Addison-Wesley Longman Ltd. Google Scholar
Jian, F.-F., Ren, X.-Y., Qin, Y.-Q. & Hu, L.-H. (2007). Acta Cryst. E63, o3056. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL/PC. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar

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Volume 64| Part 1| January 2008| Page o138

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