

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810044442/cv2783sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810044442/cv2783Isup2.hkl |
CCDC reference: 803103
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.029
- wR factor = 0.124
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers . 4
Alert level C PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 5 PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc) 4
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.02 From the CIF: _reflns_number_total 1477 Count of symmetry unique reflns 919 Completeness (_total/calc) 160.72% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 558 Fraction of Friedel pairs measured 0.607 Are heavy atom types Z>Si present yes PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large. 0.11 PLAT916_ALERT_2_G Hooft y and Flack x Parameter values differ by . 0.21
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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).
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).
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].
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).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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).
![]() | Fig. 1. View of (I) showing the atom-labelling scheme and 35% probability displacement ellipsoids [symmetry code: (A) = -x,-y + 1,z]. |
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 |
Rigaku Saturn CCD area-detector diffractometer | 1477 independent reflections |
Radiation source: rotating anode | 1421 reflections with I > 2σ(I) |
Confocal monochromator | 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 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 = 1.03 | 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 | Absolute structure parameter: 0.16 (14) |
C17H12N4S4 | V = 848.9 (3) Å3 |
Mr = 400.55 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 10.805 (2) Å | µ = 0.57 mm−1 |
b = 19.287 (4) Å | T = 113 K |
c = 4.0738 (8) Å | 0.20 × 0.18 × 0.10 mm |
Rigaku Saturn CCD area-detector diffractometer | 1477 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1421 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.945 | Rint = 0.028 |
6754 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.124 | Δρmax = 0.54 e Å−3 |
S = 1.03 | Δρmin = −0.55 e Å−3 |
1477 reflections | Absolute structure: Flack (1983), 554 Friedel pairs |
115 parameters | Absolute structure parameter: 0.16 (14) |
0 restraints |
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. |
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 |
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 |
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 code: (i) −x, −y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C17H12N4S4 |
Mr | 400.55 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 113 |
a, b, c (Å) | 10.805 (2), 19.287 (4), 4.0738 (8) |
V (Å3) | 848.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.57 |
Crystal size (mm) | 0.20 × 0.18 × 0.10 |
Data collection | |
Diffractometer | Rigaku Saturn CCD area-detector |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.895, 0.945 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6754, 1477, 1421 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.124, 1.03 |
No. of reflections | 1477 |
No. of parameters | 115 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.55 |
Absolute structure | Flack (1983), 554 Friedel pairs |
Absolute structure parameter | 0.16 (14) |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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].