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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2483.
Published online 2009 September 16. doi:  10.1107/S1600536809036782
PMCID: PMC2970373

Bis(1,3,4-thia­diazol-2-yl) disulfide

Abstract

The title compound, C4H2N4S4, lies about a twofold rotation axis situated at the mid-point of the central S—S bond. Each of two thia­diazole rings is essentially planar, with an rms deviation for the unique thia­diazole ring plane of 0.0019 (7) Å. C—H(...)N hydrogen bonds link adjacent mol­ecules, forming zigzag chains along the c axis. In addition, these chains are connected by inter­molecular S(...)S inter­actions [S(...)S = 3.5153 (11) Å] , forming corrugated sheets, and further fabricate a three-dimensional supra­molecular structure by inter­molecular N(...)S contacts [S(...)N = 3.1941 (17) Å].

Related literature

For potential applications of thia­diazo­les, see: Coyanis et al. (2002 [triangle]); Wang & Cao (2005 [triangle]). For their use as ligands in transition-metal coordination chemistry, see: Huang et al. (2004 [triangle]); Zheng et al. (2005 [triangle]). For the structure of bis­(2-methyl-1,3,4-thia­diazol­yl)-5,5′-disulfide, see: Hipler et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2483-scheme1.jpg

Experimental

Crystal data

  • C4H2N4S4
  • M r = 234.34
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2483-efi1.jpg
  • a = 9.706 (2) Å
  • b = 4.8980 (12) Å
  • c = 18.008 (5) Å
  • β = 100.074 (3)°
  • V = 842.9 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.07 mm−1
  • T = 291 K
  • 0.29 × 0.20 × 0.11 mm

Data collection

  • Bruker SMART CCD area detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.746, T max = 0.889
  • 2915 measured reflections
  • 783 independent reflections
  • 727 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.055
  • S = 1.11
  • 783 reflections
  • 55 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036782/sj2643sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036782/sj2643Isup2.hkl

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

Acknowledgments

This work was supported by the Natural Science Foundation of China (grant No. 20872058).

supplementary crystallographic information

Comment

Thiadiazoles have attracted increasing attention because of their potential applications in pharmaceutical, agricultural, industrial, coordination and polymer chemistry (Coyanis et al., 2002, Wang & Cao, 2005). Ligands involving thiadiazole group have also shown interesting coordination chemistry with transition metal ions (Huang et al., 2004; Zheng et al., 2005). Exploring the applications of thiadiazole derivatives as ligands for metal complexation, we report here the synthesis and structure of bis(1,3,4-thiadiazolyl)5,5'-disulfide (I), a new and potentially multi-functional ligand (Fig. 1).

The title compound,C4H2N4S4, lies about a twofold rotation axis situated at the mid-point of the central S–S bond. Each of the thiadiazole rings is essentially planar, with an rms deviation for the unique thiadiazole ring plane of 0.0019 (7)Å. The dihedral angle and centroid-centroid distance between the two thiadaizole rings are 86.64 (44)° and 5.25 (14) Å, respectively. The N1-C1 and N2-C2 bond lengths, 1.298 (2) Å and 1.290 (2) Å, respectively, indicate significant double bond character, which is very similar to the structure of bis(2-methyl-1,3,4-thiadiazolyl)-5,5'-disulfide (Hipler,et al., 2003).

In the crystal structure, molecules of (I) form 1-dimensional zigzag chains by way of weak intermolecular C-H···N hydrogen bonds along the c axis (Fig.3). In addition, these chains are linked by intermolecular S···S interactions [S2···S1 = 3.5153 (11) Å] to form corrugated sheets (Fig. 3). Further intermolecular N···S interactions (S2···N1 = 3.1941 (17) Å] generate a 3-dimensional supramolecular network structure (Fig. 4).

Experimental

The title compound was prepared by adding hydrogen peroxide (30%, 10.4 mL) drop-wise to a solution of 2-mercapto-1,3,4-thiadiazole (0.2 mol) in ethanol (30 mL) and water (20 mL) at room temperature. The mixture was then refluxed for 6 h. The reaction mixture was taken up in hexane (100 mL), washed with water and brine, and dried with Na2SO4. The solvent was removed under reduced pressure, and the crude product was recrystallised from ethanol to give the title compound as colourless solid in 85% yield. Colorless block-like single crystals were obtained by slow evaporation from ethanol at room temperature.

Refinement

The H atoms were positioned geometrically and treated as riding with d(C-H) = 0.93Å, Uiso=1.2Ueq (C)

Figures

Fig. 1.
View of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
The 1-dimensional zigzag chain formed by intermolecular C-H···N interactions, shown as dashed lines.
Fig. 3.
Corrugated sheets formed by intermolecular C-H···N and S···S interactions, shown as dashed lines.
Fig. 4.
The 3-dimensional network structure formed by intermolecular C–H···N, S···S and N···S interactions, shown as dashed lines.

Crystal data

C4H2N4S4F(000) = 472
Mr = 234.34Dx = 1.847 Mg m3
Monoclinic, C2/cMelting point: 384 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 9.706 (2) ÅCell parameters from 1881 reflections
b = 4.8980 (12) Åθ = 2.3–28.3°
c = 18.008 (5) ŵ = 1.07 mm1
β = 100.074 (3)°T = 291 K
V = 842.9 (4) Å3Block, colorless
Z = 40.29 × 0.20 × 0.11 mm

Data collection

Bruker SMART CCD area detector diffractometer783 independent reflections
Radiation source: fine-focus sealed tube727 reflections with I > 2σ(I)
graphiteRint = 0.017
[var phi] and ω scansθmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −11→11
Tmin = 0.746, Tmax = 0.889k = −5→5
2915 measured reflectionsl = −21→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.0269P)2 + 0.5364P] where P = (Fo2 + 2Fc2)/3
783 reflections(Δ/σ)max = 0.001
55 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = −0.26 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S10.58334 (4)0.20034 (8)0.72250 (2)0.03599 (15)
S20.37175 (4)0.60103 (10)0.63157 (3)0.04226 (16)
C10.53518 (15)0.4548 (3)0.65306 (8)0.0291 (3)
C20.43894 (19)0.7877 (4)0.56554 (9)0.0393 (4)
H20.38580.91530.53470.047*
N10.62594 (14)0.5425 (3)0.61357 (8)0.0388 (3)
N20.56803 (16)0.7391 (3)0.56152 (8)0.0414 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0434 (3)0.0342 (3)0.0334 (2)0.00958 (17)0.01497 (18)0.00365 (16)
S20.0290 (2)0.0495 (3)0.0495 (3)0.00302 (18)0.01012 (19)0.0138 (2)
C10.0310 (8)0.0296 (8)0.0274 (7)0.0002 (6)0.0072 (6)−0.0023 (6)
C20.0433 (10)0.0400 (10)0.0333 (9)−0.0019 (7)0.0034 (7)0.0067 (7)
N10.0358 (8)0.0441 (8)0.0390 (8)0.0026 (6)0.0137 (6)0.0069 (6)
N20.0463 (9)0.0443 (8)0.0354 (7)−0.0022 (7)0.0118 (6)0.0079 (6)

Geometric parameters (Å, °)

S1—C11.7695 (16)C1—N11.298 (2)
S1—S1i2.0393 (9)C2—N21.290 (2)
S2—C21.7164 (17)C2—H20.9300
S2—C11.7217 (16)N1—N21.392 (2)
C1—S1—S1i102.08 (5)N2—C2—S2115.54 (13)
C2—S2—C186.01 (8)N2—C2—H2122.2
N1—C1—S2115.22 (12)S2—C2—H2122.2
N1—C1—S1119.96 (12)C1—N1—N2111.40 (13)
S2—C1—S1124.81 (9)C2—N2—N1111.82 (14)
C2—S2—C1—N1−0.11 (13)S2—C1—N1—N2−0.16 (18)
C2—S2—C1—S1−179.53 (11)S1—C1—N1—N2179.30 (11)
S1i—S1—C1—N1169.70 (12)S2—C2—N2—N1−0.5 (2)
S1i—S1—C1—S2−10.90 (11)C1—N1—N2—C20.4 (2)
C1—S2—C2—N20.38 (15)

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···N2ii0.932.523.249 (2)136

Symmetry codes: (ii) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2643).

References

  • Bruker (1997). SMART, SAINT and SADABS Bruker AXS Inc., Madison,Wisconsin, USA.
  • Coyanis, E. M., Boese, R., Autino, J. C., Romano, R. M. & Della Védova, C. O. (2002). J. Phys. Org. Chem.16, 1–8.
  • Hipler, F., Winter, M. & Fischer, R. A. (2003). J. Mol. Struct.658, 179–191.
  • Huang, Z., Du, M., Song, H. B. & Bu, X. H. (2004). Cryst. Growth Des.4, 71–78.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, D. Z. & Cao, L. H. (2005). Chem. Res. Chin. Univ.21, 172–176.
  • Zheng, Y., Li, J. R., Du, M., Zou, R. Q. & Bu, X. H. (2005). Cryst. Growth Des.5, 215–222.

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