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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o138.
Published online 2007 December 6. doi:  10.1107/S1600536807062848
PMCID: PMC2915207

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

Abstract

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 [triangle]); Jian et al. (2007 [triangle]).

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Object name is e-64-0o138-scheme1.jpg

Experimental

Crystal data

  • C7H8N5S+·Cl
  • M r = 229.69
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o138-efi1.jpg
  • 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[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.089
  • S = 0.87
  • 2301 reflections
  • 140 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 1997b [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062848/at2512Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms of the amine group and H5B bonded to C5 were found from difference Fourier map and refined freely. The other H atoms were fixed 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=1.2Ueq of the parent atoms.

Figures

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

Crystal data

C7H8N5S+·ClF000 = 472
Mr = 229.69Dx = 1.600 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
a = 7.2290 (14) ÅCell parameters from 25 reflections
b = 12.922 (3) Åθ = 4–14º
c = 11.253 (4) ŵ = 0.59 mm1
β = 114.90 (2)ºT = 293 (2) K
V = 953.5 (4) Å3Black, yellow
Z = 40.20 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.017
Radiation source: fine-focus sealed tubeθmax = 28.3º
Monochromator: graphiteθmin = 2.5º
T = 293(2) Kh = −6→9
ω scansk = −17→16
Absorption correction: nonel = −14→14
6085 measured reflections3 standard reflections
2301 independent reflections every 100 reflections
2071 reflections with I > 2σ(I) intensity decay: none

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.029  w = 1/[σ2(Fo2) + (0.0625P)2 + 0.3755P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.089(Δ/σ)max < 0.001
S = 0.87Δρmax = 0.33 e Å3
2301 reflectionsΔρmin = −0.24 e Å3
140 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (2)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
Cl10.21801 (6)−0.06699 (3)−0.00811 (4)0.04580 (14)
S10.27272 (7)−0.39138 (3)−0.07565 (4)0.04812 (14)
N10.5768 (2)−0.45060 (10)−0.20638 (17)0.0452 (3)
N20.52602 (18)−0.34784 (9)−0.19273 (11)0.0338 (3)
N30.41277 (19)−0.21399 (9)−0.13746 (12)0.0389 (3)
H3A0.3507−0.1739−0.10510.047*
N40.5307 (2)−0.17818 (9)−0.19636 (12)0.0388 (3)
N50.9097 (2)−0.33194 (10)−0.40767 (12)0.0410 (3)
H5A0.9391−0.3863−0.44040.049*
C10.9917 (2)−0.24258 (13)−0.41851 (16)0.0437 (3)
H1C1.0785−0.2393−0.46030.052*
C20.9465 (3)−0.15530 (13)−0.36718 (18)0.0497 (4)
H2A1.0010−0.0918−0.37470.060*
C30.8196 (2)−0.16212 (12)−0.30438 (16)0.0431 (3)
H3B0.7896−0.1032−0.26850.052*
C40.7363 (2)−0.25703 (10)−0.29446 (13)0.0332 (3)
C50.7842 (2)−0.34241 (11)−0.34905 (14)0.0386 (3)
C60.5992 (2)−0.26159 (10)−0.22922 (13)0.0326 (3)
C70.4025 (2)−0.31668 (11)−0.13467 (13)0.0346 (3)
H5B0.738 (3)−0.4045 (15)−0.3468 (18)0.045 (5)*
H1A0.569 (3)−0.4851 (18)−0.142 (2)0.061 (6)*
H1B0.476 (3)−0.4713 (16)−0.279 (2)0.052 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0618 (3)0.0326 (2)0.0622 (3)0.00315 (15)0.0448 (2)0.00064 (14)
S10.0556 (3)0.0435 (2)0.0606 (3)0.00530 (16)0.0394 (2)0.00822 (16)
N10.0599 (8)0.0267 (6)0.0637 (9)0.0062 (6)0.0405 (8)0.0028 (6)
N20.0410 (6)0.0273 (5)0.0391 (6)0.0041 (4)0.0227 (5)−0.0006 (4)
N30.0475 (7)0.0340 (6)0.0448 (6)0.0052 (5)0.0289 (6)−0.0025 (5)
N40.0492 (7)0.0314 (6)0.0448 (7)0.0030 (5)0.0285 (6)−0.0026 (5)
N50.0513 (7)0.0378 (6)0.0430 (7)0.0076 (5)0.0288 (6)−0.0008 (5)
C10.0441 (8)0.0484 (8)0.0478 (8)0.0044 (6)0.0284 (7)0.0042 (6)
C20.0540 (9)0.0391 (8)0.0680 (10)−0.0043 (7)0.0372 (8)0.0002 (7)
C30.0486 (8)0.0328 (7)0.0561 (9)−0.0003 (6)0.0300 (7)−0.0056 (6)
C40.0365 (6)0.0324 (6)0.0334 (6)0.0031 (5)0.0173 (5)−0.0008 (5)
C50.0513 (8)0.0306 (7)0.0423 (7)0.0020 (6)0.0280 (6)−0.0007 (5)
C60.0382 (7)0.0294 (6)0.0329 (6)0.0021 (5)0.0176 (5)−0.0016 (5)
C70.0379 (7)0.0353 (7)0.0342 (6)0.0054 (5)0.0185 (5)0.0009 (5)

Geometric parameters (Å, °)

S1—C71.6667 (15)N5—C51.3339 (19)
N1—N21.4032 (16)N5—H5A0.8600
N1—H1A0.87 (2)C1—C21.368 (2)
N1—H1B0.88 (2)C1—H1C0.9300
N2—C61.3686 (17)C2—C31.376 (2)
N2—C71.3703 (17)C2—H2A0.9300
N3—C71.3302 (19)C3—C41.391 (2)
N3—N41.3625 (17)C3—H3B0.9300
N3—H3A0.8600C4—C51.3762 (19)
N4—C61.3029 (17)C4—C61.4622 (19)
N5—C11.327 (2)C5—H5B0.874 (19)
N2—N1—H1A106.4 (15)C1—C2—H2A120.2
N2—N1—H1B103.6 (14)C3—C2—H2A120.2
H1A—N1—H1B107 (2)C2—C3—C4120.16 (14)
C6—N2—C7108.38 (11)C2—C3—H3B119.9
C6—N2—N1125.86 (12)C4—C3—H3B119.9
C7—N2—N1125.69 (12)C5—C4—C3118.15 (13)
C7—N3—N4113.76 (11)C5—C4—C6122.90 (13)
C7—N3—H3A123.1C3—C4—C6118.94 (12)
N4—N3—H3A123.1N5—C5—C4119.39 (14)
C6—N4—N3104.32 (12)N5—C5—H5B117.2 (13)
C1—N5—C5123.85 (13)C4—C5—H5B123.4 (13)
C1—N5—H5A118.1N4—C6—N2110.35 (12)
C5—N5—H5A118.1N4—C6—C4121.86 (12)
N5—C1—C2118.87 (14)N2—C6—C4127.79 (12)
N5—C1—H1C120.6N3—C7—N2103.17 (12)
C2—C1—H1C120.6N3—C7—S1129.32 (11)
C1—C2—C3119.57 (15)N2—C7—S1127.51 (11)
C7—N3—N4—C6−1.15 (17)C7—N2—C6—C4180.00 (13)
C5—N5—C1—C2−0.1 (2)N1—N2—C6—C42.9 (2)
N5—C1—C2—C30.8 (3)C5—C4—C6—N4−169.13 (14)
C1—C2—C3—C4−0.7 (3)C3—C4—C6—N49.6 (2)
C2—C3—C4—C5−0.1 (2)C5—C4—C6—N211.6 (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—N21.52 (16)
C3—C4—C5—N50.8 (2)N4—N3—C7—S1−178.52 (11)
C6—C4—C5—N5179.58 (13)C6—N2—C7—N3−1.28 (15)
N3—N4—C6—N20.25 (15)N1—N2—C7—N3175.79 (14)
N3—N4—C6—C4−179.13 (12)C6—N2—C7—S1178.76 (11)
C7—N2—C6—N40.67 (16)N1—N2—C7—S1−4.2 (2)
N1—N2—C6—N4−176.40 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···Cl10.862.213.0715 (13)175
N5—H5A···Cl1i0.862.513.1740 (14)135
N5—H5A···Cl1ii0.862.553.1999 (15)133
N1—H1A···S1iii0.87 (2)2.74 (2)3.5381 (19)153.4 (18)
N1—H1B···Cl1iv0.88 (2)2.51 (2)3.300 (2)149.5 (18)
N1—H1B···N4ii0.88 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2512).

References

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography