Abstract
The asymmetric unit of the title compound, C17H12N4S4, contains one half-molecule situated on a twofold rotational axis. In the molecule, the thiadiazole and attached phenyl rings are twisted by 5.8 (3)°.
Related literature
For biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996 ▶); Wang et al. (1999 ▶); Carvalho et al. (2004 ▶); Riente et al. (2009 ▶); Poorrajab et al. (2009 ▶).
Experimental
Crystal data
C17H12N4S4
M r = 400.55
Orthorhombic,
a = 10.805 (2) Å
b = 19.287 (4) Å
c = 4.0738 (8) Å
V = 848.9 (3) Å3
Z = 2
Mo Kα radiation
μ = 0.57 mm−1
T = 113 K
0.20 × 0.18 × 0.10 mm
Data collection
Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.895, T max = 0.945
6754 measured reflections
1477 independent reflections
1421 reflections with I > 2σ(I)
R int = 0.028
Refinement
R[F 2 > 2σ(F 2)] = 0.029
wR(F 2) = 0.124
S = 1.03
1477 reflections
115 parameters
H-atom parameters constrained
Δρmax = 0.54 e Å−3
Δρmin = −0.55 e Å−3
Absolute structure: Flack (1983 ▶), 554 Friedel pairs
Flack parameter: 0.16 (14)
Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.
Supplementary Material
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810044442/cv2783sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044442/cv2783Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
We thank the Doctoral Foundation of Huanggang Normal University (grant No. 09CD155).
supplementary crystallographic information
Comment
1,3,4-Thiadiazole derivatives attracted considerable attention due to their broad spectrum of chemical and pharmaceutical properties (Nakagawa et al., 1996; Wang et al., 1999), with particular attention being paid to the anti-trypanosomal activities of Megazol and related compounds (Carvalho et al., 2004; Riente et al., 2009; Poorrajab et al., 2009). Herewith we report the synthesis and crystal structure of the title compound, (I), a new 1,3,4-thiadiazole derivative.
The molecular structure of (I) is shown in Fig.1. In the crystal structure, the molecule is situated on a two-fold rotational axis so asymmetric unit contains a half of the molecule. 1,3,4-Thiadiazole ring is planar with an r.m.s. deviation of 0.0048 (2)Å and maximum deviation of 0.0072 (2)Å for atom C7. The dihedral angle between the thiadiazole and attached phenyl rings is 5.8 (3)°. As a result of π-π conjugation, the Csp2-S bond length [S2—C8 = 1.751 (3) Å] is significantly shorter than the Csp3-S bond length [S2—C9 = 1.810 (2) Å].
Experimental
A suspension of 5-diphenyl-1,3,4-thiadiazol-2-thiol (2.0 mmol) and 1,1-dibromomethane (1.0 mmol) in ethanol (10 ml) was stirred at room temperature. The reaction progress was monitored via TLC. The resulting precipitate was filtered off, washed with cold ethanol, dried and purified to give the target product as light yellow solid in 95% yield. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-ethanol (1:1).
Refinement
All H atoms were positioned geometrically and refined as riding (C—H = 0.95–0.99 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(parent).
Figures
Fig. 1.
View of (I) showing the atom-labelling scheme and 35% probability displacement ellipsoids [symmetry code: (A) = -x,-y + 1,z].
Crystal data
| C17H12N4S4 | F(000) = 412 |
| Mr = 400.55 | Dx = 1.567 Mg m−3 |
| Orthorhombic, P21212 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2 2ab | Cell parameters from 2856 reflections |
| a = 10.805 (2) Å | θ = 2.1–27.9° |
| b = 19.287 (4) Å | µ = 0.57 mm−1 |
| c = 4.0738 (8) Å | T = 113 K |
| V = 848.9 (3) Å3 | Prism, colourless |
| Z = 2 | 0.20 × 0.18 × 0.10 mm |
Data collection
| Rigaku Saturn CCD area-detector diffractometer | 1477 independent reflections |
| Radiation source: rotating anode | 1421 reflections with I > 2σ(I) |
| confocal | Rint = 0.028 |
| Detector resolution: 7.31 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
| φ and ω scans | h = −12→12 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −22→22 |
| Tmin = 0.895, Tmax = 0.945 | l = −4→4 |
| 6754 measured reflections |
Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.110P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.124 | (Δ/σ)max = 0.001 |
| S = 1.02 | Δρmax = 0.54 e Å−3 |
| 1477 reflections | Δρmin = −0.55 e Å−3 |
| 115 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.049 (10) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 554 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: 0.16 (14) |
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)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| S1 | 0.19317 (6) | 0.33910 (3) | 0.3294 (2) | 0.0215 (3) | |
| S2 | 0.13644 (6) | 0.47579 (4) | 0.6577 (2) | 0.0216 (3) | |
| N1 | −0.0251 (2) | 0.29797 (13) | 0.4770 (7) | 0.0223 (6) | |
| N2 | −0.0161 (2) | 0.36481 (13) | 0.6002 (7) | 0.0231 (6) | |
| C1 | −0.0141 (3) | 0.16581 (16) | 0.1495 (9) | 0.0260 (7) | |
| H1 | −0.0904 | 0.1795 | 0.2453 | 0.031* | |
| C2 | −0.0048 (3) | 0.10272 (16) | −0.0079 (9) | 0.0289 (8) | |
| H2 | −0.0748 | 0.0731 | −0.0206 | 0.035* | |
| C3 | 0.1073 (3) | 0.08236 (15) | −0.1485 (9) | 0.0279 (7) | |
| H3 | 0.1136 | 0.0389 | −0.2568 | 0.033* | |
| C4 | 0.2085 (3) | 0.12546 (15) | −0.1299 (9) | 0.0262 (7) | |
| H4 | 0.2847 | 0.1117 | −0.2264 | 0.031* | |
| C5 | 0.1999 (3) | 0.18852 (16) | 0.0284 (8) | 0.0234 (7) | |
| H5 | 0.2704 | 0.2178 | 0.0420 | 0.028* | |
| C6 | 0.0885 (3) | 0.20960 (14) | 0.1682 (8) | 0.0196 (6) | |
| C7 | 0.0747 (2) | 0.27771 (15) | 0.3277 (7) | 0.0181 (6) | |
| C8 | 0.0919 (3) | 0.39217 (14) | 0.5395 (8) | 0.0192 (7) | |
| C9 | 0.0000 | 0.5000 | 0.8888 (11) | 0.0229 (10) | |
| H9A | 0.0223 | 0.5394 | 1.0330 | 0.027* | 0.50 |
| H9B | −0.0223 | 0.4606 | 1.0330 | 0.027* | 0.50 |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0163 (4) | 0.0229 (4) | 0.0252 (5) | −0.0010 (3) | 0.0012 (4) | −0.0011 (3) |
| S2 | 0.0221 (4) | 0.0204 (4) | 0.0223 (5) | −0.0011 (3) | −0.0018 (4) | 0.0005 (3) |
| N1 | 0.0199 (12) | 0.0197 (12) | 0.0273 (14) | 0.0005 (9) | −0.0006 (12) | 0.0018 (12) |
| N2 | 0.0229 (12) | 0.0200 (12) | 0.0263 (15) | 0.0006 (10) | 0.0035 (11) | −0.0007 (12) |
| C1 | 0.0198 (14) | 0.0279 (15) | 0.0303 (18) | 0.0002 (11) | 0.0039 (16) | 0.0029 (17) |
| C2 | 0.0258 (14) | 0.0254 (15) | 0.036 (2) | −0.0019 (12) | −0.0060 (17) | −0.0012 (16) |
| C3 | 0.0374 (17) | 0.0206 (13) | 0.0257 (17) | 0.0052 (13) | 0.0029 (17) | −0.0019 (15) |
| C4 | 0.0244 (14) | 0.0254 (14) | 0.0289 (18) | 0.0079 (12) | 0.0013 (15) | 0.0031 (16) |
| C5 | 0.0208 (14) | 0.0232 (14) | 0.0260 (17) | 0.0012 (12) | −0.0002 (15) | 0.0041 (14) |
| C6 | 0.0189 (14) | 0.0209 (14) | 0.0191 (15) | 0.0028 (11) | −0.0046 (13) | 0.0043 (14) |
| C7 | 0.0162 (13) | 0.0216 (13) | 0.0166 (14) | 0.0000 (11) | −0.0015 (13) | 0.0033 (13) |
| C8 | 0.0206 (14) | 0.0198 (12) | 0.0170 (15) | 0.0038 (11) | −0.0010 (13) | −0.0001 (12) |
| C9 | 0.029 (2) | 0.0235 (19) | 0.016 (2) | −0.0003 (17) | 0.000 | 0.000 |
Geometric parameters (Å, °)
| S1—C8 | 1.726 (3) | C2—H2 | 0.9500 |
| S1—C7 | 1.744 (3) | C3—C4 | 1.376 (5) |
| S2—C8 | 1.751 (3) | C3—H3 | 0.9500 |
| S2—C9 | 1.810 (2) | C4—C5 | 1.380 (5) |
| N1—C7 | 1.298 (4) | C4—H4 | 0.9500 |
| N1—N2 | 1.387 (4) | C5—C6 | 1.391 (4) |
| N2—C8 | 1.304 (4) | C5—H5 | 0.9500 |
| C1—C2 | 1.379 (5) | C6—C7 | 1.473 (4) |
| C1—C6 | 1.396 (4) | C9—S2i | 1.810 (2) |
| C1—H1 | 0.9500 | C9—H9A | 0.9900 |
| C2—C3 | 1.396 (4) | C9—H9B | 0.9900 |
| C8—S1—C7 | 86.51 (14) | C4—C5—H5 | 119.8 |
| C8—S2—C9 | 99.02 (10) | C6—C5—H5 | 119.8 |
| C7—N1—N2 | 113.0 (2) | C5—C6—C1 | 119.2 (3) |
| C8—N2—N1 | 111.8 (2) | C5—C6—C7 | 121.9 (3) |
| C2—C1—C6 | 120.1 (3) | C1—C6—C7 | 118.9 (3) |
| C2—C1—H1 | 119.9 | N1—C7—C6 | 124.0 (3) |
| C6—C1—H1 | 119.9 | N1—C7—S1 | 113.8 (2) |
| C1—C2—C3 | 120.1 (3) | C6—C7—S1 | 122.2 (2) |
| C1—C2—H2 | 119.9 | N2—C8—S1 | 114.9 (2) |
| C3—C2—H2 | 119.9 | N2—C8—S2 | 124.5 (2) |
| C4—C3—C2 | 119.8 (3) | S1—C8—S2 | 120.57 (17) |
| C4—C3—H3 | 120.1 | S2—C9—S2i | 117.3 (2) |
| C2—C3—H3 | 120.1 | S2—C9—H9A | 108.0 |
| C3—C4—C5 | 120.3 (3) | S2i—C9—H9A | 108.0 |
| C3—C4—H4 | 119.9 | S2—C9—H9B | 108.0 |
| C5—C4—H4 | 119.9 | S2i—C9—H9B | 108.0 |
| C4—C5—C6 | 120.5 (3) | H9A—C9—H9B | 107.2 |
| C7—N1—N2—C8 | −0.5 (4) | C1—C6—C7—N1 | 5.7 (5) |
| C6—C1—C2—C3 | 0.1 (5) | C5—C6—C7—S1 | 4.3 (4) |
| C1—C2—C3—C4 | 0.0 (5) | C1—C6—C7—S1 | −173.9 (3) |
| C2—C3—C4—C5 | 0.3 (6) | C8—S1—C7—N1 | −1.1 (2) |
| C3—C4—C5—C6 | −0.6 (5) | C8—S1—C7—C6 | 178.6 (3) |
| C4—C5—C6—C1 | 0.7 (5) | N1—N2—C8—S1 | −0.4 (3) |
| C4—C5—C6—C7 | −177.6 (3) | N1—N2—C8—S2 | 179.9 (2) |
| C2—C1—C6—C5 | −0.4 (5) | C7—S1—C8—N2 | 0.8 (3) |
| C2—C1—C6—C7 | 177.9 (3) | C7—S1—C8—S2 | −179.5 (2) |
| N2—N1—C7—C6 | −178.6 (2) | C9—S2—C8—N2 | 4.3 (3) |
| N2—N1—C7—S1 | 1.1 (3) | C9—S2—C8—S1 | −175.34 (19) |
| C5—C6—C7—N1 | −176.0 (3) | C8—S2—C9—S2i | −76.74 (11) |
Symmetry codes: (i) −x, −y+1, z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2783).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810044442/cv2783sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044442/cv2783Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report