Bis(4H-1,2,4-triazol-3-yl)disulfane

Liu, D.; Xu, Y.; Li, X.; Ying, S.; Chen, W.

doi:10.1107/S1600536807065452

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o247

https://doi.org/10.1107/S1600536807065452

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Bis(4H-1,2,4-triazol-3-yl)disulfane

Dongsheng Liu,^a ^* Yaping Xu,^a Xinfa Li,^a Shaoming Ying ^a and Wentong Chen ^a

^aDepartment of Chemistry, JingGangShan University, Ji'an, Jiangxi 343009, People's Republic of China
^*Correspondence e-mail: liudongsheng@jgsu.edu.cn

(Received 30 October 2007; accepted 4 December 2007; online 12 December 2007)

The title compound, C₄H₄N₆S₂, was synthesized by the reaction of 3-mercapto-1H-1,2,4-triazole with sodium hydroxide in ethanol. The molecule possesses a crystallographically imposed twofold axis. Intermolecular N—H⋯N hydrogen bonds link the molecules into chains along the c axis.

Related literature

For related literature, see: De Luca (2006 ); Di Santo, Tafi, Costi, Botta, Artico, Corelli, Forte, Caporuscio, Angiolella & Palamara (2005 ); Fringuelli et al. (2005 ); Menozzi et al. (2004 ).

Experimental

Crystal data

C₄H₄N₆S₂
M_r = 200.25
Monoclinic, C 2/c
a = 14.052 (3) Å
b = 6.4044 (13) Å
c = 9.928 (2) Å
β = 122.18 (3)°
V = 756.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 293 (2) K
0.12 × 0.09 × 0.06 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.932, T_max = 0.962
3518 measured reflections
859 independent reflections
742 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.081
S = 1.09
859 reflections
63 parameters
All H-atom parameters refined
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.89 (2)	1.97 (2)	2.8617 (19)	174.9 (19)
Symmetry code: (i) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: RAPID-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1993 ); software used to prepare material for publication: SHELXL97 (Sheldrick,1997).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807065452/rz2177sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807065452/rz2177Isup2.hkl

checkCIF report

Comment top

It is well known that derivatives of pyrazole, imidazole, triazole, tetrazole and indole exhibit extensive biological activities (De Luca, 2006; Fringuelli et al., 2005; Di Santo et al., 2005; Menozzi et al., 2004). In a search for more efficient antibacterial medicines, we have synthesized a new azole derivative and its crystal structure is reported here.

In the molecule of the title compound (Fig. 1), which possesses a crystallographically imposed twofold axis, the torsion angles C1—S1—S1ⁱ—C1ⁱ and S1ⁱ—S1—C1—N3 are 83.69 (8) and -93.69 (13)°, respectively [symmetry code: (i) -x, y, -0.5 - z]. The dihedral angle formed by the triazole rings is 21.80 (7)°. In the crystal structure (Fig. 2 and 3), molecules are linked by N—H···N hydrogen bonding interactions (Table 1) to form stepped chains running parallel to the c axis.

Related literature top

For related literature, see: De Luca (2006); Di Santo, Tafi, Costi, Botta, Artico, Corelli, Forte, Caporuscio, Angiolella & Palamara (2005); Fringuelli et al. (2005); Menozzi et al. (2004).

Experimental top

3-Mercapto-1H-1,2,4-triazole (0.025 mol, 5.05 g) and sodium hydroxide (0.025 mol, 1.01 g) were dissolved in ethanol (15 ml). The mixture was refluxed at 353 K for five hours, cooled to room temperature, acidified with HCl (12 M) and filtered. Colourless crystal of the title compound were obtained on slow evaporation of the solvent after several days at room temperature.

Structure description top

For related literature, see: De Luca (2006); Di Santo, Tafi, Costi, Botta, Artico, Corelli, Forte, Caporuscio, Angiolella & Palamara (2005); Fringuelli et al. (2005); Menozzi et al. (2004).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: RAPID-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1993); software used to prepare material for publication: SHELXL97 (Sheldrick,1997).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x, y, -z - 1/2]
	Fig. 2. The chain of hydrogen-bonded molecules running along the c axis. Hydrogen bonding interactions are shown as red dashed lines.
	Fig. 3. Packing diagram of the title compound viewed along the c axis.

Bis(4H-1,2,4-triazol-3-yl)disulfane top

Crystal data top

C₄H₄N₆S₂	F(000) = 408
M_r = 200.25	D_x = 1.759 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 14.052 (3) Å	θ = 12–18°
b = 6.4044 (13) Å	µ = 0.65 mm⁻¹
c = 9.928 (2) Å	T = 293 K
β = 122.18 (3)°	Block, colourless
V = 756.2 (4) Å³	0.12 × 0.09 × 0.06 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	859 independent reflections
Radiation source: fine-focus sealed tube	742 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Oscillation scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
T_min = 0.932, T_max = 0.962	k = −8→7
3518 measured reflections	l = −12→12

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	All H-atom parameters refined
S = 1.09	w = 1/[σ²(F_o²) + (0.0491P)²] where P = (F_o² + 2F_c²)/3
859 reflections	(Δ/σ)_max < 0.001
63 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₄H₄N₆S₂	V = 756.2 (4) Å³
M_r = 200.25	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.052 (3) Å	µ = 0.65 mm⁻¹
b = 6.4044 (13) Å	T = 293 K
c = 9.928 (2) Å	0.12 × 0.09 × 0.06 mm
β = 122.18 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	859 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	742 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.962	R_int = 0.035
3518 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.081	All H-atom parameters refined
S = 1.09	Δρ_max = 0.25 e Å⁻³
859 reflections	Δρ_min = −0.22 e Å⁻³
63 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
S1	0.08684 (3)	0.07452 (6)	−0.17828 (4)	0.03333 (18)
N1	0.13246 (12)	0.4379 (2)	0.15290 (16)	0.0330 (3)
N2	0.11117 (12)	0.2436 (2)	0.08916 (15)	0.0350 (3)
N3	0.13151 (11)	0.4757 (2)	−0.06502 (15)	0.0315 (3)
C1	0.11097 (11)	0.2743 (2)	−0.04273 (16)	0.0275 (3)
C2	0.14361 (13)	0.5723 (3)	0.06089 (18)	0.0331 (4)
H1	0.1365 (17)	0.462 (4)	0.244 (3)	0.053 (6)*
H2	0.1600 (16)	0.725 (3)	0.083 (2)	0.042 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0383 (3)	0.0327 (3)	0.0299 (3)	0.00536 (14)	0.0188 (2)	−0.00149 (13)
N1	0.0378 (7)	0.0423 (8)	0.0238 (7)	0.0035 (5)	0.0197 (6)	−0.0008 (5)
N2	0.0434 (7)	0.0387 (8)	0.0284 (7)	0.0037 (5)	0.0228 (6)	0.0035 (5)
N3	0.0383 (7)	0.0365 (7)	0.0258 (7)	−0.0025 (5)	0.0212 (6)	−0.0017 (5)
C1	0.0280 (7)	0.0346 (8)	0.0215 (7)	0.0031 (5)	0.0143 (6)	0.0022 (5)
C2	0.0357 (8)	0.0387 (9)	0.0270 (8)	−0.0029 (6)	0.0181 (7)	−0.0034 (6)

Geometric parameters (Å, º) top

S1—C1	1.7541 (15)	N2—C1	1.3225 (19)
S1—S1ⁱ	2.0693 (11)	N3—C2	1.322 (2)
N1—C2	1.324 (2)	N3—C1	1.3653 (19)
N1—N2	1.3549 (18)	C2—H2	1.004 (19)
N1—H1	0.89 (2)

C1—S1—S1ⁱ	101.72 (5)	N2—C1—N3	114.30 (13)
C2—N1—N2	110.63 (13)	N2—C1—S1	123.30 (12)
C2—N1—H1	128.6 (15)	N3—C1—S1	122.40 (11)
N2—N1—H1	120.8 (15)	N3—C2—N1	110.21 (15)
C1—N2—N1	102.11 (13)	N3—C2—H2	124.4 (12)
C2—N3—C1	102.74 (13)	N1—C2—H2	125.4 (12)

Symmetry code: (i) −x, y, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱⁱ	0.89 (2)	1.97 (2)	2.8617 (19)	174.9 (19)

Symmetry code: (ii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₄N₆S₂
M_r	200.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.052 (3), 6.4044 (13), 9.928 (2)
β (°)	122.18 (3)
V (Å³)	756.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.12 × 0.09 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.932, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	3518, 859, 742
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.081, 1.09
No. of reflections	859
No. of parameters	63
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22

Computer programs: RAPID-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1993), SHELXL97 (Sheldrick,1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.89 (2)	1.97 (2)	2.8617 (19)	174.9 (19)

Symmetry code: (i) x, −y+1, z+1/2.

Acknowledgements

This work was supported financially by the Natural Science Project of Jinggangshan University (JZ0731).

References

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