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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)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810044442/cv2783sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536810044442/cv2783Isup2.hkl
Contains datablock I

CCDC reference: 803103

Key indicators

  • Single-crystal X-ray study
  • T = 113 K
  • Mean [sigma](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

Comment top

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].

Related literature top

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 top

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 top

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).

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of (I) showing the atom-labelling scheme and 35% probability displacement ellipsoids [symmetry code: (A) = -x,-y + 1,z].
Bis[(5-phenyl-1,3,4-thiadiazol-2-yl)sulfanyl]methane top
Crystal data top
C17H12N4S4F(000) = 412
Mr = 400.55Dx = 1.567 Mg m3
Orthorhombic, P21212Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 2856 reflections
a = 10.805 (2) Åθ = 2.1–27.9°
b = 19.287 (4) ŵ = 0.57 mm1
c = 4.0738 (8) ÅT = 113 K
V = 848.9 (3) Å3Prism, colourless
Z = 20.20 × 0.18 × 0.10 mm
Data collection top
Rigaku Saturn CCD area-detector
diffractometer
1477 independent reflections
Radiation source: rotating anode1421 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.028
Detector resolution: 7.31 pixels mm-1θmax = 25.0°, θmin = 2.1°
φ and ω scansh = 1212
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)
k = 2222
Tmin = 0.895, Tmax = 0.945l = 44
6754 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.03Δρmax = 0.54 e Å3
1477 reflectionsΔρmin = 0.55 e Å3
115 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.049 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 554 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.16 (14)
Crystal data top
C17H12N4S4V = 848.9 (3) Å3
Mr = 400.55Z = 2
Orthorhombic, P21212Mo Kα radiation
a = 10.805 (2) ŵ = 0.57 mm1
b = 19.287 (4) ÅT = 113 K
c = 4.0738 (8) Å0.20 × 0.18 × 0.10 mm
Data collection top
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 = 0.945Rint = 0.028
6754 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.54 e Å3
S = 1.03Δρmin = 0.55 e Å3
1477 reflectionsAbsolute structure: Flack (1983), 554 Friedel pairs
115 parametersAbsolute structure parameter: 0.16 (14)
0 restraints
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
S10.19317 (6)0.33910 (3)0.3294 (2)0.0215 (3)
S20.13644 (6)0.47579 (4)0.6577 (2)0.0216 (3)
N10.0251 (2)0.29797 (13)0.4770 (7)0.0223 (6)
N20.0161 (2)0.36481 (13)0.6002 (7)0.0231 (6)
C10.0141 (3)0.16581 (16)0.1495 (9)0.0260 (7)
H10.09040.17950.24530.031*
C20.0048 (3)0.10272 (16)0.0079 (9)0.0289 (8)
H20.07480.07310.02060.035*
C30.1073 (3)0.08236 (15)0.1485 (9)0.0279 (7)
H30.11360.03890.25680.033*
C40.2085 (3)0.12546 (15)0.1299 (9)0.0262 (7)
H40.28470.11170.22640.031*
C50.1999 (3)0.18852 (16)0.0284 (8)0.0234 (7)
H50.27040.21780.04200.028*
C60.0885 (3)0.20960 (14)0.1682 (8)0.0196 (6)
C70.0747 (2)0.27771 (15)0.3277 (7)0.0181 (6)
C80.0919 (3)0.39217 (14)0.5395 (8)0.0192 (7)
C90.00000.50000.8888 (11)0.0229 (10)
H9A0.02230.53941.03300.027*0.50
H9B0.02230.46061.03300.027*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0163 (4)0.0229 (4)0.0252 (5)0.0010 (3)0.0012 (4)0.0011 (3)
S20.0221 (4)0.0204 (4)0.0223 (5)0.0011 (3)0.0018 (4)0.0005 (3)
N10.0199 (12)0.0197 (12)0.0273 (14)0.0005 (9)0.0006 (12)0.0018 (12)
N20.0229 (12)0.0200 (12)0.0263 (15)0.0006 (10)0.0035 (11)0.0007 (12)
C10.0198 (14)0.0279 (15)0.0303 (18)0.0002 (11)0.0039 (16)0.0029 (17)
C20.0258 (14)0.0254 (15)0.036 (2)0.0019 (12)0.0060 (17)0.0012 (16)
C30.0374 (17)0.0206 (13)0.0257 (17)0.0052 (13)0.0029 (17)0.0019 (15)
C40.0244 (14)0.0254 (14)0.0289 (18)0.0079 (12)0.0013 (15)0.0031 (16)
C50.0208 (14)0.0232 (14)0.0260 (17)0.0012 (12)0.0002 (15)0.0041 (14)
C60.0189 (14)0.0209 (14)0.0191 (15)0.0028 (11)0.0046 (13)0.0043 (14)
C70.0162 (13)0.0216 (13)0.0166 (14)0.0000 (11)0.0015 (13)0.0033 (13)
C80.0206 (14)0.0198 (12)0.0170 (15)0.0038 (11)0.0010 (13)0.0001 (12)
C90.029 (2)0.0235 (19)0.016 (2)0.0003 (17)0.0000.000
Geometric parameters (Å, º) top
S1—C81.726 (3)C2—H20.9500
S1—C71.744 (3)C3—C41.376 (5)
S2—C81.751 (3)C3—H30.9500
S2—C91.810 (2)C4—C51.380 (5)
N1—C71.298 (4)C4—H40.9500
N1—N21.387 (4)C5—C61.391 (4)
N2—C81.304 (4)C5—H50.9500
C1—C21.379 (5)C6—C71.473 (4)
C1—C61.396 (4)C9—S2i1.810 (2)
C1—H10.9500C9—H9A0.9900
C2—C31.396 (4)C9—H9B0.9900
C8—S1—C786.51 (14)C4—C5—H5119.8
C8—S2—C999.02 (10)C6—C5—H5119.8
C7—N1—N2113.0 (2)C5—C6—C1119.2 (3)
C8—N2—N1111.8 (2)C5—C6—C7121.9 (3)
C2—C1—C6120.1 (3)C1—C6—C7118.9 (3)
C2—C1—H1119.9N1—C7—C6124.0 (3)
C6—C1—H1119.9N1—C7—S1113.8 (2)
C1—C2—C3120.1 (3)C6—C7—S1122.2 (2)
C1—C2—H2119.9N2—C8—S1114.9 (2)
C3—C2—H2119.9N2—C8—S2124.5 (2)
C4—C3—C2119.8 (3)S1—C8—S2120.57 (17)
C4—C3—H3120.1S2—C9—S2i117.3 (2)
C2—C3—H3120.1S2—C9—H9A108.0
C3—C4—C5120.3 (3)S2i—C9—H9A108.0
C3—C4—H4119.9S2—C9—H9B108.0
C5—C4—H4119.9S2i—C9—H9B108.0
C4—C5—C6120.5 (3)H9A—C9—H9B107.2
C7—N1—N2—C80.5 (4)C1—C6—C7—N15.7 (5)
C6—C1—C2—C30.1 (5)C5—C6—C7—S14.3 (4)
C1—C2—C3—C40.0 (5)C1—C6—C7—S1173.9 (3)
C2—C3—C4—C50.3 (6)C8—S1—C7—N11.1 (2)
C3—C4—C5—C60.6 (5)C8—S1—C7—C6178.6 (3)
C4—C5—C6—C10.7 (5)N1—N2—C8—S10.4 (3)
C4—C5—C6—C7177.6 (3)N1—N2—C8—S2179.9 (2)
C2—C1—C6—C50.4 (5)C7—S1—C8—N20.8 (3)
C2—C1—C6—C7177.9 (3)C7—S1—C8—S2179.5 (2)
N2—N1—C7—C6178.6 (2)C9—S2—C8—N24.3 (3)
N2—N1—C7—S11.1 (3)C9—S2—C8—S1175.34 (19)
C5—C6—C7—N1176.0 (3)C8—S2—C9—S2i76.74 (11)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC17H12N4S4
Mr400.55
Crystal system, space groupOrthorhombic, P21212
Temperature (K)113
a, b, c (Å)10.805 (2), 19.287 (4), 4.0738 (8)
V3)848.9 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.57
Crystal size (mm)0.20 × 0.18 × 0.10
Data collection
DiffractometerRigaku Saturn CCD area-detector
Absorption correctionMulti-scan
(CrystalClear; Rigaku/MSC, 2005)
Tmin, Tmax0.895, 0.945
No. of measured, independent and
observed [I > 2σ(I)] reflections
6754, 1477, 1421
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.124, 1.03
No. of reflections1477
No. of parameters115
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.55
Absolute structureFlack (1983), 554 Friedel pairs
Absolute structure parameter0.16 (14)

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

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