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ISSN: 2056-9890

Bis(1,3,4-thia­diazol-2-yl) di­sulfide

aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China.
*Correspondence e-mail: zbt@lynu.edu.cn

(Received 30 August 2009; accepted 11 September 2009; online 16 September 2009)

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[Coyanis, E. M., Boese, R., Autino, J. C., Romano, R. M. & Della Védova, C. O. (2002). J. Phys. Org. Chem. 16, 1-8.]); Wang & Cao (2005[Wang, D. Z. & Cao, L. H. (2005). Chem. Res. Chin. Univ. 21, 172-176.]). For their use as ligands in transition-metal coordination chemistry, see: Huang et al. (2004[Huang, Z., Du, M., Song, H. B. & Bu, X. H. (2004). Cryst. Growth Des. 4, 71-78.]); Zheng et al. (2005[Zheng, Y., Li, J. R., Du, M., Zou, R. Q. & Bu, X. H. (2005). Cryst. Growth Des. 5, 215-222.]). For the structure of bis­(2-methyl-1,3,4-thia­diazol­yl)-5,5′-disulfide, see: Hipler et al. (2003[Hipler, F., Winter, M. & Fischer, R. A. (2003). J. Mol. Struct. 658, 179-191.]).

[Scheme 1]

Experimental

Crystal data
  • C4H2N4S4

  • Mr = 234.34

  • Monoclinic, C 2/c

  • 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[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]) Tmin = 0.746, Tmax = 0.889

  • 2915 measured reflections

  • 783 independent reflections

  • 727 reflections with I > 2σ(I)

  • Rint = 0.017

Refinement
  • R[F2 > 2σ(F2)] = 0.021

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯N2i 0.93 2.52 3.249 (2) 136
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

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

Experimental top

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 top

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

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The 1-dimensional zigzag chain formed by intermolecular C-H···N interactions, shown as dashed lines.
[Figure 3] Fig. 3. Corrugated sheets formed by intermolecular C-H···N and S···S interactions, shown as dashed lines.
[Figure 4] Fig. 4. The 3-dimensional network structure formed by intermolecular C–H···N, S···S and N···S interactions, shown as dashed lines.
Bis(1,3,4-thiadiazol-2-yl) disulfide top
Crystal data top
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 top
Bruker SMART CCD area detector
diffractometer
783 independent reflections
Radiation source: fine-focus sealed tube727 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ϕ and ω scansθmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1111
Tmin = 0.746, Tmax = 0.889k = 55
2915 measured reflectionsl = 2121
Refinement top
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 = 1.11 w = 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
Crystal data top
C4H2N4S4V = 842.9 (4) Å3
Mr = 234.34Z = 4
Monoclinic, C2/cMo Kα radiation
a = 9.706 (2) ŵ = 1.07 mm1
b = 4.8980 (12) ÅT = 291 K
c = 18.008 (5) Å0.29 × 0.20 × 0.11 mm
β = 100.074 (3)°
Data collection top
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 = 0.889Rint = 0.017
2915 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.055H-atom parameters constrained
S = 1.11Δρmax = 0.17 e Å3
783 reflectionsΔρmin = 0.26 e Å3
55 parameters
Special details top

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) top
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) top
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, º) top
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—N10.11 (13)S2—C1—N1—N20.16 (18)
C2—S2—C1—S1179.53 (11)S1—C1—N1—N2179.30 (11)
S1i—S1—C1—N1169.70 (12)S2—C2—N2—N10.5 (2)
S1i—S1—C1—S210.90 (11)C1—N1—N2—C20.4 (2)
C1—S2—C2—N20.38 (15)
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2ii0.932.523.249 (2)136
Symmetry code: (ii) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC4H2N4S4
Mr234.34
Crystal system, space groupMonoclinic, C2/c
Temperature (K)291
a, b, c (Å)9.706 (2), 4.8980 (12), 18.008 (5)
β (°) 100.074 (3)
V3)842.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.07
Crystal size (mm)0.29 × 0.20 × 0.11
Data collection
DiffractometerBruker SMART CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.746, 0.889
No. of measured, independent and
observed [I > 2σ(I)] reflections
2915, 783, 727
Rint0.017
(sin θ/λ)max1)0.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.055, 1.11
No. of reflections783
No. of parameters55
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.26

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···N2i0.932.523.249 (2)135.7
Symmetry code: (i) x+1, y+2, z+1.
 

Acknowledgements

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

References

First citationBruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.  Google Scholar
First citationCoyanis, E. M., Boese, R., Autino, J. C., Romano, R. M. & Della Védova, C. O. (2002). J. Phys. Org. Chem. 16, 1–8.  Web of Science CSD CrossRef Google Scholar
First citationHipler, F., Winter, M. & Fischer, R. A. (2003). J. Mol. Struct. 658, 179–191.  Web of Science CSD CrossRef CAS Google Scholar
First citationHuang, Z., Du, M., Song, H. B. & Bu, X. H. (2004). Cryst. Growth Des. 4, 71–78.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWang, D. Z. & Cao, L. H. (2005). Chem. Res. Chin. Univ. 21, 172–176.  CAS Google Scholar
First citationZheng, Y., Li, J. R., Du, M., Zou, R. Q. & Bu, X. H. (2005). Cryst. Growth Des. 5, 215–222.  Web of Science CSD CrossRef CAS Google Scholar

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ISSN: 2056-9890
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