Acta Cryst. (2009). E65, o2483 [ doi:10.1107/S1600536809036782 ]
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 SS interactions [SS = 3.5153 (11) Å] , forming corrugated sheets, and further fabricate a three-dimensional supramolecular structure by intermolecular NS contacts [SN = 3.1941 (17) Å].
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.
The H atoms were positioned geometrically and treated as riding with d(C-H) = 0.93Å, Uiso=1.2Ueq (C)
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./sj2643fig1thm.gif)
| Fig. 1. View of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./sj2643fig2thm.gif)
| Fig. 2. The 1-dimensional zigzag chain formed by intermolecular C-H···N interactions, shown as dashed lines. |
![[Figure 3]](./sj2643fig3thm.gif)
| Fig. 3. Corrugated sheets formed by intermolecular C-H···N and S···S interactions, shown as dashed lines. |
![[Figure 4]](./sj2643fig4thm.gif)
| Fig. 4. The 3-dimensional network structure formed by intermolecular C–H···N, S···S and N···S interactions, shown as dashed lines. |
| C4H2N4S4 | F(000) = 472 |
| Mr = 234.34 | Dx = 1.847 Mg m−3 |
| Monoclinic, C2/c | Melting point: 384 K |
| Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.706 (2) Å | Cell parameters from 1881 reflections |
| b = 4.8980 (12) Å | θ = 2.3–28.3° |
| c = 18.008 (5) Å | µ = 1.07 mm−1 |
| β = 100.074 (3)° | T = 291 K |
| V = 842.9 (4) Å3 | Block, colorless |
| Z = 4 | 0.29 × 0.20 × 0.11 mm |
| Bruker SMART CCD area detector diffractometer | 783 independent reflections |
| Radiation source: fine-focus sealed tube | 727 reflections with I > 2σ(I) |
| graphite | Rint = 0.017 |
| φ and ω scans | θmax = 25.5°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −11→11 |
| Tmin = 0.746, Tmax = 0.889 | k = −5→5 |
| 2915 measured reflections | l = −21→21 |
| 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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.055 | H-atom parameters constrained |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0269P)2 + 0.5364P] where P = (Fo2 + 2Fc2)/3 |
| 783 reflections | (Δ/σ)max = 0.001 |
| 55 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.26 e Å−3 |
| C4H2N4S4 | V = 842.9 (4) Å3 |
| Mr = 234.34 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 9.706 (2) Å | µ = 1.07 mm−1 |
| b = 4.8980 (12) Å | T = 291 K |
| c = 18.008 (5) Å | 0.29 × 0.20 × 0.11 mm |
| β = 100.074 (3)° |
| Bruker SMART CCD area detector diffractometer | 783 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | 727 reflections with I > 2σ(I) |
| Tmin = 0.746, Tmax = 0.889 | Rint = 0.017 |
| 2915 measured reflections | θmax = 25.5° |
| R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
| wR(F2) = 0.055 | Δρmax = 0.17 e Å−3 |
| S = 1.11 | Δρmin = −0.26 e Å−3 |
| 783 reflections | Absolute structure: ? |
| 55 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.58334 (4) | 0.20034 (8) | 0.72250 (2) | 0.03599 (15) | |
| S2 | 0.37175 (4) | 0.60103 (10) | 0.63157 (3) | 0.04226 (16) | |
| C1 | 0.53518 (15) | 0.4548 (3) | 0.65306 (8) | 0.0291 (3) | |
| C2 | 0.43894 (19) | 0.7877 (4) | 0.56554 (9) | 0.0393 (4) | |
| H2 | 0.3858 | 0.9153 | 0.5347 | 0.047* | |
| N1 | 0.62594 (14) | 0.5425 (3) | 0.61357 (8) | 0.0388 (3) | |
| N2 | 0.56803 (16) | 0.7391 (3) | 0.56152 (8) | 0.0414 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0434 (3) | 0.0342 (3) | 0.0334 (2) | 0.00958 (17) | 0.01497 (18) | 0.00365 (16) |
| S2 | 0.0290 (2) | 0.0495 (3) | 0.0495 (3) | 0.00302 (18) | 0.01012 (19) | 0.0138 (2) |
| C1 | 0.0310 (8) | 0.0296 (8) | 0.0274 (7) | 0.0002 (6) | 0.0072 (6) | −0.0023 (6) |
| C2 | 0.0433 (10) | 0.0400 (10) | 0.0333 (9) | −0.0019 (7) | 0.0034 (7) | 0.0067 (7) |
| N1 | 0.0358 (8) | 0.0441 (8) | 0.0390 (8) | 0.0026 (6) | 0.0137 (6) | 0.0069 (6) |
| N2 | 0.0463 (9) | 0.0443 (8) | 0.0354 (7) | −0.0022 (7) | 0.0118 (6) | 0.0079 (6) |
| S1—C1 | 1.7695 (16) | C1—N1 | 1.298 (2) |
| S1—S1i | 2.0393 (9) | C2—N2 | 1.290 (2) |
| S2—C2 | 1.7164 (17) | C2—H2 | 0.9300 |
| S2—C1 | 1.7217 (16) | N1—N2 | 1.392 (2) |
| C1—S1—S1i | 102.08 (5) | N2—C2—S2 | 115.54 (13) |
| C2—S2—C1 | 86.01 (8) | N2—C2—H2 | 122.2 |
| N1—C1—S2 | 115.22 (12) | S2—C2—H2 | 122.2 |
| N1—C1—S1 | 119.96 (12) | C1—N1—N2 | 111.40 (13) |
| S2—C1—S1 | 124.81 (9) | C2—N2—N1 | 111.82 (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—N2 | 179.30 (11) |
| S1i—S1—C1—N1 | 169.70 (12) | S2—C2—N2—N1 | −0.5 (2) |
| S1i—S1—C1—S2 | −10.90 (11) | C1—N1—N2—C2 | 0.4 (2) |
| C1—S2—C2—N2 | 0.38 (15) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···N2ii | 0.93 | 2.52 | 3.249 (2) | 136 |
| Symmetry codes: (ii) −x+1, −y+2, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···N2i | 0.93 | 2.52 | 3.249 (2) | 136 |
| Symmetry codes: (i) −x+1, −y+2, −z+1. |
This work was supported by the Natural Science Foundation of China (grant No. 20872058).
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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).