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Acta Crystallogr Sect E Struct Rep Online. 2012 March 1; 68(Pt 3): o851.
Published online 2012 February 24. doi:  10.1107/S1600536812007520
PMCID: PMC3297906

2-(4-Methyl­phen­yl)-5-[({[5-(4-methyl­phen­yl)-1,3,4-thia­diazol-2-yl]sulfan­yl}meth­yl)sulfan­yl]-1,3,4-thia­diazole

Abstract

In the title compound, C19H16N4S4, the mol­ecules exhibit a butterfly conformation, where the thia­diazole and attached benzene rings in two wings are almost coplanar, with dihedral angles of 0.8 (3) and 0.9 (3)°, respectively, while the two thia­diazole rings form a dihedral angle of 46.3 (3)°.

Related literature  

For the biological properties of 1,3,4-thia­diazole derivatives, see: Nakagawa et al. (1996 [triangle]); Wang et al. (1999 [triangle]); Carvalho et al. (2004 [triangle]). For the crystal structures of related compounds, see: Li et al. (2011 [triangle]); Wang et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-0o851-scheme1.jpg

Experimental  

Crystal data  

  • C19H16N4S4
  • M r = 428.60
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-0o851-efi1.jpg
  • a = 16.8944 (14) Å
  • b = 4.1959 (5) Å
  • c = 27.107 (2) Å
  • β = 96.084 (8)°
  • V = 1910.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.51 mm−1
  • T = 113 K
  • 0.50 × 0.04 × 0.04 mm

Data collection  

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.785, T max = 0.980
  • 14969 measured reflections
  • 4535 independent reflections
  • 2927 reflections with I > 2σ(I)
  • R int = 0.094

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.142
  • S = 0.96
  • 4535 reflections
  • 246 parameters
  • H-atom parameters constrained
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.60 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812007520/cv5245sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007520/cv5245Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007520/cv5245Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

1,3,4-Thiadiazole derivatives are important for medicinal chemistry due to their chemical and pharmaceutical properties (Nakagawa et al., 1996; Wang et al., 1999; Carvalho et al., 2004). Similar crystal structures of the 1,3,4-thiadiazole derivatives have been reported . As a part of our research, the title compound (I) has been synthesized, and herewith we present its crystal structure.

In (I) (Fig. 1), all geometric parameters are normal and comparable with those reported for related 1,3,4-thiadiazole derivatives (Li et al., 2011; Wang et al., 2010). Two thiadiazole rings form a dihedral angle of 46.3 (3)%. The dihedral angles between the benzene rings and attached thiadiazole rings are 0.8 (3) and 0.9 (3)° indicating the two rings are almost parallel. The same situation has been observed in the crystal structure of 1,4-bis(5-phenyl-1,3,4-thiadiazol-2-ylsulfanyl)butane (Li et al., 2011).

Experimental

The title compound was synthesized by the reaction of the 1,1-dibromomethane (1.0 mmol) and 5-tolyl-1,3,4-thiadiazol-2-thiol (2.0 mmol) in ethanol (20 ml) at room temperature. Crystals of (I) suitable for single-crystal X-ray analysis were grown by slow evaporation of a solution in chloroform-enthanol (1:1).

Refinement

All H atoms were positioned geometrically and refined as riding (C—H = 0.95 - 0.99 Å), with Uiso(H) = 1.2 - 1.5Ueq (C).

Figures

Fig. 1.
View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 60% probability level.

Crystal data

C19H16N4S4F(000) = 888
Mr = 428.60Dx = 1.490 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5461 reflections
a = 16.8944 (14) Åθ = 1.4–27.8°
b = 4.1959 (5) ŵ = 0.51 mm1
c = 27.107 (2) ÅT = 113 K
β = 96.084 (8)°Prism, colourless
V = 1910.7 (3) Å30.50 × 0.04 × 0.04 mm
Z = 4

Data collection

Rigaku Saturn CCD area-detector diffractometer4535 independent reflections
Radiation source: rotating anode2927 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.094
Detector resolution: 14.22 pixels mm-1θmax = 27.8°, θmin = 1.4°
[var phi] and ω scansh = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −5→4
Tmin = 0.785, Tmax = 0.980l = −35→31
14969 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H-atom parameters constrained
S = 0.96w = 1/[σ2(Fo2) + (0.0566P)2] where P = (Fo2 + 2Fc2)/3
4535 reflections(Δ/σ)max = 0.001
246 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = −0.60 e Å3

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)

xyzUiso*/Ueq
S10.41711 (5)0.77165 (19)−0.01333 (3)0.0266 (2)
S20.39123 (5)1.1072 (2)0.08165 (3)0.0282 (2)
S30.26282 (5)1.06832 (19)0.15267 (3)0.0270 (2)
S40.33462 (5)1.07934 (19)0.26002 (3)0.0268 (2)
N10.26848 (16)0.6479 (6)−0.02748 (10)0.0285 (6)
N20.27897 (16)0.8187 (6)0.01681 (10)0.0288 (6)
N30.39960 (17)1.3525 (6)0.18983 (10)0.0292 (6)
N40.44931 (16)1.4137 (6)0.23312 (10)0.0289 (6)
C10.3546 (2)−0.0838 (8)−0.23078 (12)0.0349 (8)
H1A0.3223−0.2782−0.23130.052*
H1B0.4101−0.1403−0.23410.052*
H1C0.33430.0547−0.25840.052*
C20.3500 (2)0.0891 (7)−0.18231 (12)0.0263 (7)
C30.4179 (2)0.2240 (8)−0.15616 (12)0.0296 (8)
H30.46800.2007−0.16870.036*
C40.4135 (2)0.3902 (7)−0.11251 (12)0.0283 (7)
H40.46020.4807−0.09550.034*
C50.34068 (19)0.4251 (7)−0.09335 (11)0.0237 (7)
C60.27246 (19)0.2897 (7)−0.11872 (12)0.0268 (7)
H60.22250.3126−0.10600.032*
C70.2776 (2)0.1227 (7)−0.16224 (12)0.0275 (7)
H70.23090.0289−0.17880.033*
C80.33463 (19)0.6019 (7)−0.04729 (11)0.0242 (7)
C90.35275 (19)0.8994 (7)0.02832 (11)0.0255 (7)
C100.2996 (2)1.2661 (7)0.10072 (12)0.0277 (7)
H10A0.30801.49390.10920.033*
H10B0.25811.25510.07210.033*
C110.33781 (19)1.1814 (7)0.19861 (12)0.0247 (7)
C120.42392 (18)1.2861 (7)0.27270 (12)0.0258 (7)
C130.46511 (19)1.3186 (7)0.32295 (12)0.0262 (7)
C140.43531 (19)1.1764 (8)0.36363 (12)0.0278 (7)
H140.38721.05800.35910.033*
C150.4755 (2)1.2068 (8)0.41067 (12)0.0292 (7)
H150.45401.10960.43800.035*
C160.54653 (19)1.3758 (7)0.41906 (12)0.0285 (7)
C170.5753 (2)1.5225 (8)0.37799 (12)0.0286 (7)
H170.62311.64340.38260.034*
C180.53548 (19)1.4947 (8)0.33077 (12)0.0279 (7)
H180.55621.59610.30350.033*
C190.5928 (2)1.3981 (9)0.46959 (12)0.0346 (8)
H19A0.63981.26020.47080.052*
H19B0.55901.32940.49490.052*
H19C0.60961.61900.47600.052*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0174 (4)0.0334 (5)0.0289 (4)−0.0015 (3)0.0025 (3)−0.0022 (4)
S20.0207 (4)0.0359 (5)0.0279 (4)−0.0021 (3)0.0019 (3)−0.0029 (4)
S30.0204 (4)0.0320 (5)0.0285 (4)−0.0002 (3)0.0022 (3)−0.0018 (3)
S40.0197 (4)0.0329 (5)0.0279 (4)−0.0018 (3)0.0022 (3)0.0007 (3)
N10.0230 (15)0.0343 (16)0.0279 (14)0.0008 (12)0.0014 (12)−0.0048 (12)
N20.0242 (15)0.0342 (16)0.0282 (14)0.0000 (12)0.0035 (12)−0.0044 (12)
N30.0228 (15)0.0352 (16)0.0296 (14)−0.0016 (12)0.0026 (12)0.0011 (12)
N40.0211 (15)0.0357 (16)0.0297 (15)−0.0025 (12)0.0013 (12)0.0020 (12)
C10.034 (2)0.037 (2)0.0336 (19)0.0041 (16)0.0044 (16)−0.0033 (16)
C20.0266 (18)0.0262 (17)0.0261 (16)0.0032 (14)0.0024 (14)0.0034 (13)
C30.0204 (17)0.0360 (19)0.0332 (18)0.0014 (14)0.0064 (15)0.0030 (15)
C40.0199 (17)0.0312 (18)0.0332 (18)−0.0029 (14)0.0003 (14)−0.0010 (14)
C50.0209 (17)0.0231 (16)0.0262 (16)0.0013 (13)−0.0009 (13)0.0034 (13)
C60.0203 (17)0.0292 (17)0.0311 (17)0.0002 (13)0.0035 (14)0.0023 (14)
C70.0214 (17)0.0306 (18)0.0303 (17)−0.0017 (14)0.0012 (14)−0.0005 (14)
C80.0196 (16)0.0231 (16)0.0290 (16)0.0002 (13)−0.0020 (13)0.0030 (13)
C90.0230 (17)0.0279 (17)0.0261 (16)0.0001 (14)0.0045 (14)0.0043 (14)
C100.0249 (18)0.0283 (17)0.0290 (17)0.0051 (14)−0.0019 (14)−0.0024 (14)
C110.0185 (16)0.0265 (17)0.0291 (16)0.0049 (13)0.0034 (13)0.0005 (13)
C120.0151 (16)0.0272 (17)0.0355 (18)0.0012 (13)0.0041 (14)−0.0025 (14)
C130.0169 (16)0.0276 (17)0.0342 (18)0.0044 (13)0.0029 (14)−0.0012 (14)
C140.0156 (16)0.0309 (18)0.0371 (18)0.0004 (13)0.0028 (14)−0.0020 (15)
C150.0217 (17)0.0355 (19)0.0308 (17)−0.0002 (14)0.0044 (14)−0.0010 (15)
C160.0193 (17)0.0306 (18)0.0350 (18)0.0046 (14)0.0001 (14)−0.0035 (15)
C170.0169 (16)0.0317 (18)0.0373 (19)0.0002 (14)0.0027 (14)−0.0037 (15)
C180.0210 (17)0.0300 (17)0.0329 (17)0.0012 (14)0.0043 (14)−0.0028 (15)
C190.0221 (18)0.046 (2)0.0344 (18)0.0029 (15)−0.0023 (15)−0.0011 (16)

Geometric parameters (Å, º)

S1—C91.733 (3)C4—H40.9500
S1—C81.739 (3)C5—C61.398 (4)
S2—C91.753 (3)C5—C81.465 (4)
S2—C101.810 (3)C6—C71.383 (4)
S3—C111.745 (3)C6—H60.9500
S3—C101.801 (3)C7—H70.9500
S4—C111.725 (3)C10—H10A0.9900
S4—C121.743 (3)C10—H10B0.9900
N1—C81.304 (4)C12—C131.469 (4)
N1—N21.393 (4)C13—C141.394 (4)
N2—C91.297 (4)C13—C181.397 (4)
N3—C111.310 (4)C14—C151.386 (4)
N3—N41.393 (4)C14—H140.9500
N4—C121.311 (4)C15—C161.391 (4)
C1—C21.510 (4)C15—H150.9500
C1—H1A0.9800C16—C171.403 (5)
C1—H1B0.9800C16—C191.506 (4)
C1—H1C0.9800C17—C181.386 (5)
C2—C71.398 (4)C17—H170.9500
C2—C31.403 (4)C18—H180.9500
C3—C41.382 (4)C19—H19A0.9800
C3—H30.9500C19—H19B0.9800
C4—C51.393 (4)C19—H19C0.9800
C9—S1—C887.06 (15)S1—C9—S2119.18 (19)
C9—S2—C1099.51 (15)S3—C10—S2115.46 (17)
C11—S3—C1098.52 (15)S3—C10—H10A108.4
C11—S4—C1287.24 (15)S2—C10—H10A108.4
C8—N1—N2113.2 (3)S3—C10—H10B108.4
C9—N2—N1111.9 (3)S2—C10—H10B108.4
C11—N3—N4111.6 (3)H10A—C10—H10B107.5
C12—N4—N3113.2 (3)N3—C11—S4114.7 (2)
C2—C1—H1A109.5N3—C11—S3123.5 (2)
C2—C1—H1B109.5S4—C11—S3121.77 (18)
H1A—C1—H1B109.5N4—C12—C13123.9 (3)
C2—C1—H1C109.5N4—C12—S4113.2 (2)
H1A—C1—H1C109.5C13—C12—S4123.0 (2)
H1B—C1—H1C109.5C14—C13—C18118.6 (3)
C7—C2—C3117.7 (3)C14—C13—C12121.2 (3)
C7—C2—C1121.0 (3)C18—C13—C12120.1 (3)
C3—C2—C1121.3 (3)C15—C14—C13120.3 (3)
C4—C3—C2121.4 (3)C15—C14—H14119.8
C4—C3—H3119.3C13—C14—H14119.8
C2—C3—H3119.3C14—C15—C16121.9 (3)
C3—C4—C5120.2 (3)C14—C15—H15119.1
C3—C4—H4119.9C16—C15—H15119.1
C5—C4—H4119.9C15—C16—C17117.3 (3)
C4—C5—C6119.2 (3)C15—C16—C19122.4 (3)
C4—C5—C8121.0 (3)C17—C16—C19120.3 (3)
C6—C5—C8119.8 (3)C18—C17—C16121.4 (3)
C7—C6—C5120.2 (3)C18—C17—H17119.3
C7—C6—H6119.9C16—C17—H17119.3
C5—C6—H6119.9C17—C18—C13120.4 (3)
C6—C7—C2121.3 (3)C17—C18—H18119.8
C6—C7—H7119.3C13—C18—H18119.8
C2—C7—H7119.3C16—C19—H19A109.5
N1—C8—C5124.5 (3)C16—C19—H19B109.5
N1—C8—S1113.2 (2)H19A—C19—H19B109.5
C5—C8—S1122.3 (2)C16—C19—H19C109.5
N2—C9—S1114.6 (2)H19A—C19—H19C109.5
N2—C9—S2126.2 (3)H19B—C19—H19C109.5
C8—N1—N2—C91.0 (4)C11—S3—C10—S267.8 (2)
C11—N3—N4—C120.4 (4)C9—S2—C10—S3104.05 (19)
C7—C2—C3—C4−1.3 (5)N4—N3—C11—S4−0.1 (3)
C1—C2—C3—C4178.2 (3)N4—N3—C11—S3178.8 (2)
C2—C3—C4—C50.4 (5)C12—S4—C11—N3−0.2 (3)
C3—C4—C5—C60.1 (5)C12—S4—C11—S3−179.1 (2)
C3—C4—C5—C8−179.6 (3)C10—S3—C11—N3−2.0 (3)
C4—C5—C6—C70.2 (5)C10—S3—C11—S4176.80 (19)
C8—C5—C6—C7179.9 (3)N3—N4—C12—C13−179.3 (3)
C5—C6—C7—C2−1.0 (5)N3—N4—C12—S4−0.6 (3)
C3—C2—C7—C61.6 (5)C11—S4—C12—N40.4 (2)
C1—C2—C7—C6−177.9 (3)C11—S4—C12—C13179.2 (3)
N2—N1—C8—C5178.9 (3)N4—C12—C13—C14−179.8 (3)
N2—N1—C8—S1−0.9 (3)S4—C12—C13—C141.6 (4)
C4—C5—C8—N1179.1 (3)N4—C12—C13—C180.3 (5)
C6—C5—C8—N1−0.7 (5)S4—C12—C13—C18−178.3 (2)
C4—C5—C8—S1−1.2 (4)C18—C13—C14—C15−0.8 (5)
C6—C5—C8—S1179.1 (2)C12—C13—C14—C15179.3 (3)
C9—S1—C8—N10.4 (2)C13—C14—C15—C16−0.5 (5)
C9—S1—C8—C5−179.4 (3)C14—C15—C16—C171.5 (5)
N1—N2—C9—S1−0.7 (3)C14—C15—C16—C19−177.1 (3)
N1—N2—C9—S2−178.4 (2)C15—C16—C17—C18−1.3 (5)
C8—S1—C9—N20.2 (3)C19—C16—C17—C18177.4 (3)
C8—S1—C9—S2178.1 (2)C16—C17—C18—C130.0 (5)
C10—S2—C9—N2−16.9 (3)C14—C13—C18—C171.0 (5)
C10—S2—C9—S1165.53 (19)C12—C13—C18—C17−179.1 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV5245).

References

  • Carvalho, S. A., da Silva, E. F., Santa-Rita, R. M., de Castro, S. L. & Fraga, C. A. M. (2004). Bioorg. Med. Chem. Lett. 14, 5967–5970. [PubMed]
  • Li, S., Zhang, J., Jia, X., Gao, Y. & Wang, W. (2011). Acta Cryst. E67, o681. [PMC free article] [PubMed]
  • Nakagawa, Y., Nishimura, K., Izumi, K., Kinoshita, K., Kimura, T. & Kurihara, N. (1996). J. Pestic. Sci. 21, 195–201.
  • Rigaku/MSC (2005). CrystalClear Molecular Structure Corporation, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, Y. G., Cao, L., Yan, J., Ye, W. F., Zhou, Q. C. & Lu, B. X. (1999). Chem. J. Chin. Univ. 20, 1903–1905.
  • Wang, H., Gao, Y. & Wang, W. (2010). Acta Cryst. E66, o3085. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography