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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1668.
Published online 2009 June 24. doi:  10.1107/S1600536809023447
PMCID: PMC2969456

(E)-5-Phenyl-N-(2-thienylmethyl­ene)-1,3,4-thia­diazole-2-amine

Abstract

In the title compound, C13H9N3S2, the thio­phene and phenyl rings are oriented at dihedral angles of 8.00 (7) and 6.31 (7)°, respectively, with respect to the central thia­diazole ring. No significant C—H(...)S and π–π inter­actions exist in the crystal structure.

Related literature

For the biological activity of [1,3,4]-thia­diazole-containing compounds, see: Foroumadi, Soltani et al. (2003 [triangle]); Foroumadi, Mansouri et al. (2003 [triangle]); Holla et al. (2002 [triangle]); Genc & Servi (2005 [triangle]); Servi et al. (2005 [triangle]). For a related structure, see: Dege et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1668-scheme1.jpg

Experimental

Crystal data

  • C13H9N3S2
  • M r = 271.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1668-efi1.jpg
  • a = 6.2238 (3) Å
  • b = 7.7393 (3) Å
  • c = 25.6959 (13) Å
  • β = 94.701 (4)°
  • V = 1233.55 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.41 mm−1
  • T = 293 K
  • 0.74 × 0.48 × 0.16 mm

Data collection

  • Stoe IPDS-2 diffractometer
  • Absorption correction: integration (X-RED; Stoe & Cie, 2002 [triangle]) T min = 0.815, T max = 0.943
  • 10930 measured reflections
  • 2619 independent reflections
  • 2275 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.080
  • S = 1.05
  • 2619 reflections
  • 176 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON (Spek, 2009 [triangle]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023447/ci2829sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023447/ci2829Isup2.hkl

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

Acknowledgments

The authors thank the Ondokuz Mayis University Research Fund for financial support for this study.

supplementary crystallographic information

Comment

[1,3,4]-Thiadiazoles and their derivatives exhibit diverse biological activites possibly due to the presence of ═N—C—S moiety (Holla et al., 2002; Servi et al., 2005; Genc & Servi, 2005). Various phenyl substituted [1,3,4]-thiazole-2-amines and their derivatives have recently received significant importance because of their diverse biological properties (Foroumadi, Soltani et al., 2003; Foroumadi, Mansouri et al., 2003).We report here the crystal structure of the title compound, (I).

In (I), the C7—S1 [1.7234 (13) Å] distance is shorter than the C8—S1 distance [1.7411 (13) Å]. The C11–S2 distance of 1.6993 (17) Å is shorter the C10—S2 distance of 1.7229 (13) Å and other C—S bonds in the molecule. These bond distances agree well with the corresponding values reported for 1-(thiophen-2-ylmethyl)-2-(thiophen-2-yl)-1H- benzimidazole (Dege et al., 2006). The thiophene and phenyl rings are oriented at dihedral angles of 8.00 (7)° and 6.31 (7)°, respectively, with respect to the central thiadiazole ring.

No significant C—H···S and π-π interactions are observed.

Experimental

A solution of 5-phenyl-1,3,4-thiadiazole-2-amine (0.01 mol) in absolute ethanol (20 ml) was added in small portions to a solution of thiophen-2-carbaldehyde (0.01 mol) in absolute ethanol (30 ml). The reaction mixture was maintained at 343 K for 4 h, cooled and then added to ice-cold water. The resulting solid was washed with water, dried and recrystallized from ethanol (yield 77%). IR (cm-1): 3078 (Ar H), 1633 (C═C), 1589 (C═N); 1H-NMR: 7.2–7.9 (m, 8H, aromatic protons), 9.2 (s, 1H, N═CH proton).

Refinement

Atoms H1, H9 and H12 were located in a difference map and refined freely. The other H atoms were positioned geometrically and refined using a riding model, with C-H = 0.93 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C13H9N3S2F(000) = 560
Mr = 271.35Dx = 1.461 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 17067 reflections
a = 6.2238 (3) Åθ = 1.6–26.8°
b = 7.7393 (3) ŵ = 0.41 mm1
c = 25.6959 (13) ÅT = 293 K
β = 94.701 (4)°Plate, yellow
V = 1233.55 (10) Å30.74 × 0.48 × 0.16 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer2619 independent reflections
Radiation source: fine-focus sealed tube2275 reflections with I > 2σ(I)
plane graphiteRint = 0.020
Detector resolution: 6.67 pixels mm-1θmax = 26.8°, θmin = 1.6°
ω scansh = −7→7
Absorption correction: integration (X-RED; Stoe & Cie, 2002)k = −9→9
Tmin = 0.815, Tmax = 0.943l = −32→32
10930 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.080w = 1/[σ2(Fo2) + (0.0481P)2 + 0.1148P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2619 reflectionsΔρmax = 0.18 e Å3
176 parametersΔρmin = −0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.002634 (11)

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
C10.0290 (2)0.1603 (2)0.57838 (6)0.0543 (3)
C20.0105 (3)0.0893 (2)0.62710 (6)0.0615 (4)
H20.13110.08170.65090.074*
C3−0.1859 (3)0.0297 (2)0.64059 (6)0.0621 (4)
H3−0.1976−0.01900.67330.075*
C4−0.3643 (2)0.0422 (2)0.60563 (6)0.0627 (4)
H4−0.49670.00140.61470.075*
C5−0.3479 (2)0.1152 (2)0.55709 (6)0.0565 (3)
H5−0.46980.12470.53380.068*
C6−0.1503 (2)0.17452 (16)0.54281 (5)0.0461 (3)
C7−0.13539 (19)0.24791 (17)0.49053 (5)0.0466 (3)
C8−0.0473 (2)0.36506 (18)0.40911 (5)0.0500 (3)
C90.2276 (2)0.46866 (18)0.36247 (5)0.0500 (3)
C100.3030 (2)0.55163 (17)0.31753 (5)0.0480 (3)
C110.3279 (3)0.7018 (2)0.23422 (6)0.0643 (4)
H110.30780.75410.20160.077*
C120.5205 (3)0.6920 (2)0.26256 (7)0.0631 (4)
C130.5080 (2)0.60554 (18)0.31021 (6)0.0547 (3)
H130.62590.58690.33420.066*
N1−0.30366 (19)0.27346 (19)0.45777 (5)0.0656 (4)
N2−0.25288 (19)0.3405 (2)0.41099 (5)0.0674 (4)
N30.02776 (18)0.43483 (15)0.36467 (4)0.0530 (3)
S10.10458 (5)0.30465 (5)0.466131 (13)0.04910 (12)
S20.12673 (6)0.60757 (5)0.265024 (14)0.06061 (14)
H90.333 (3)0.444 (2)0.3905 (6)0.065 (4)*
H10.158 (3)0.206 (2)0.5694 (7)0.071 (5)*
H120.645 (3)0.736 (3)0.2497 (8)0.086 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0472 (7)0.0616 (8)0.0537 (7)−0.0008 (6)0.0013 (6)−0.0007 (6)
C20.0579 (8)0.0733 (10)0.0520 (8)0.0033 (7)−0.0038 (6)0.0016 (7)
C30.0714 (9)0.0656 (9)0.0502 (8)0.0040 (7)0.0103 (7)0.0006 (7)
C40.0557 (8)0.0725 (10)0.0617 (9)−0.0027 (7)0.0151 (7)−0.0015 (7)
C50.0455 (7)0.0690 (9)0.0549 (8)0.0005 (6)0.0033 (6)−0.0047 (7)
C60.0460 (6)0.0435 (7)0.0486 (6)0.0036 (5)0.0032 (5)−0.0061 (5)
C70.0425 (6)0.0452 (6)0.0516 (7)0.0016 (5)0.0007 (5)−0.0035 (5)
C80.0466 (7)0.0514 (7)0.0509 (7)0.0011 (5)−0.0026 (5)0.0001 (6)
C90.0513 (7)0.0494 (7)0.0483 (7)0.0046 (6)−0.0021 (5)−0.0003 (6)
C100.0496 (7)0.0469 (7)0.0467 (7)0.0051 (5)−0.0010 (5)−0.0019 (5)
C110.0729 (10)0.0655 (9)0.0537 (8)−0.0013 (7)0.0004 (7)0.0108 (7)
C120.0590 (8)0.0636 (10)0.0670 (9)−0.0037 (7)0.0073 (7)0.0085 (7)
C130.0503 (7)0.0552 (8)0.0576 (8)0.0031 (6)−0.0020 (6)0.0031 (6)
N10.0443 (6)0.0864 (9)0.0647 (8)−0.0049 (6)−0.0039 (5)0.0167 (7)
N20.0479 (6)0.0901 (10)0.0622 (7)−0.0051 (6)−0.0068 (5)0.0208 (7)
N30.0518 (6)0.0564 (7)0.0499 (6)−0.0003 (5)−0.0009 (5)0.0045 (5)
S10.04071 (18)0.0581 (2)0.04783 (19)0.00331 (13)−0.00016 (12)0.00054 (14)
S20.0538 (2)0.0724 (3)0.0536 (2)−0.00062 (16)−0.00781 (15)0.00514 (17)

Geometric parameters (Å, °)

C1—C21.381 (2)C8—N31.3787 (18)
C1—C61.3875 (19)C8—S11.7411 (13)
C1—H10.923 (18)C9—N31.2770 (18)
C2—C31.377 (2)C9—C101.4335 (19)
C2—H20.93C9—H90.952 (16)
C3—C41.374 (2)C10—C131.3697 (19)
C3—H30.93C10—S21.7229 (13)
C4—C51.380 (2)C11—C121.353 (2)
C4—H40.93C11—S21.6993 (17)
C5—C61.3900 (19)C11—H110.93
C5—H50.93C12—C131.403 (2)
C6—C71.4684 (19)C12—H120.929 (19)
C7—N11.3039 (17)C13—H130.93
C7—S11.7234 (13)N1—N21.3696 (19)
C8—N21.2987 (18)
C2—C1—C6120.44 (14)N2—C8—S1113.44 (11)
C2—C1—H1121.1 (12)N3—C8—S1127.22 (10)
C6—C1—H1118.3 (11)N3—C9—C10120.78 (12)
C3—C2—C1120.20 (14)N3—C9—H9122.7 (10)
C3—C2—H2119.9C10—C9—H9116.5 (10)
C1—C2—H2119.9C13—C10—C9128.09 (12)
C4—C3—C2119.90 (14)C13—C10—S2110.88 (10)
C4—C3—H3120.0C9—C10—S2120.94 (10)
C2—C3—H3120.0C12—C11—S2112.30 (12)
C3—C4—C5120.28 (14)C12—C11—H11123.9
C3—C4—H4119.9S2—C11—H11123.9
C5—C4—H4119.9C11—C12—C13112.73 (14)
C4—C5—C6120.40 (14)C11—C12—H12121.0 (13)
C4—C5—H5119.8C13—C12—H12126.3 (13)
C6—C5—H5119.8C10—C13—C12112.57 (13)
C1—C6—C5118.77 (13)C10—C13—H13123.7
C1—C6—C7121.70 (12)C12—C13—H13123.7
C5—C6—C7119.53 (12)C7—N1—N2113.15 (12)
N1—C7—C6122.79 (12)C8—N2—N1112.78 (12)
N1—C7—S1113.62 (11)C9—N3—C8120.94 (12)
C6—C7—S1123.58 (9)C7—S1—C887.01 (6)
N2—C8—N3119.33 (12)C11—S2—C1091.51 (7)
C6—C1—C2—C30.9 (2)C11—C12—C13—C10−0.5 (2)
C1—C2—C3—C4−0.5 (2)C6—C7—N1—N2−179.04 (13)
C2—C3—C4—C5−0.3 (2)S1—C7—N1—N2−0.15 (18)
C3—C4—C5—C60.9 (2)N3—C8—N2—N1−178.89 (13)
C2—C1—C6—C5−0.3 (2)S1—C8—N2—N10.45 (19)
C2—C1—C6—C7−179.40 (13)C7—N1—N2—C8−0.2 (2)
C4—C5—C6—C1−0.6 (2)C10—C9—N3—C8−175.86 (12)
C4—C5—C6—C7178.55 (14)N2—C8—N3—C9176.50 (15)
C1—C6—C7—N1−175.17 (14)S1—C8—N3—C9−2.7 (2)
C5—C6—C7—N15.7 (2)N1—C7—S1—C80.32 (12)
C1—C6—C7—S16.05 (19)C6—C7—S1—C8179.20 (12)
C5—C6—C7—S1−173.02 (11)N2—C8—S1—C7−0.44 (13)
N3—C9—C10—C13175.89 (14)N3—C8—S1—C7178.84 (13)
N3—C9—C10—S2−0.24 (19)C12—C11—S2—C10−0.24 (14)
S2—C11—C12—C130.5 (2)C13—C10—S2—C11−0.04 (12)
C9—C10—C13—C12−176.14 (14)C9—C10—S2—C11176.70 (12)
S2—C10—C13—C120.30 (17)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2829).

References

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