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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2009 Jun 24;65(Pt 7):o1668. doi: 10.1107/S1600536809023447

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

Güneş Demirtaş a, Necmi Dege a, Memet Şekerci b, Süleyman Servi b, Muharrem Dinçer a,*
PMCID: PMC2969456  PMID: 21582928

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 ▶); Foroumadi, Mansouri et al. (2003 ▶); Holla et al. (2002 ▶); Genc & Servi (2005 ▶); Servi et al. (2005 ▶). For a related structure, see: Dege et al. (2006 ▶).graphic file with name e-65-o1668-scheme1.jpg

Experimental

Crystal data

  • C13H9N3S2

  • M r = 271.35

  • Monoclinic, Inline graphic

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

Supplementary Material

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

e-65-o1668-sup1.cif (16.7KB, cif)

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

e-65-o1668-Isup2.hkl (126KB, 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.

Fig. 1.

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

Crystal data

C13H9N3S2 F(000) = 560
Mr = 271.35 Dx = 1.461 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc Cell parameters from 17067 reflections
a = 6.2238 (3) Å θ = 1.6–26.8°
b = 7.7393 (3) Å µ = 0.41 mm−1
c = 25.6959 (13) Å T = 293 K
β = 94.701 (4)° Plate, yellow
V = 1233.55 (10) Å3 0.74 × 0.48 × 0.16 mm
Z = 4
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Data collection

Stoe IPDS-2 diffractometer 2619 independent reflections
Radiation source: fine-focus sealed tube 2275 reflections with I > 2σ(I)
plane graphite Rint = 0.020
Detector resolution: 6.67 pixels mm-1 θmax = 26.8°, θmin = 1.6°
ω scans h = −7→7
Absorption correction: integration (X-RED; Stoe & Cie, 2002) k = −9→9
Tmin = 0.815, Tmax = 0.943 l = −32→32
10930 measured reflections
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Refinement

Refinement on F2 Secondary atom site location: difference Fourier map
Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026 H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.080 w = 1/[σ2(Fo2) + (0.0481P)2 + 0.1148P] where P = (Fo2 + 2Fc2)/3
S = 1.05 (Δ/σ)max = 0.001
2619 reflections Δρmax = 0.18 e Å−3
176 parameters Δρmin = −0.17 e Å−3
0 restraints Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods Extinction coefficient: 0.002634 (11)
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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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
C1 0.0290 (2) 0.1603 (2) 0.57838 (6) 0.0543 (3)
C2 0.0105 (3) 0.0893 (2) 0.62710 (6) 0.0615 (4)
H2 0.1311 0.0817 0.6509 0.074*
C3 −0.1859 (3) 0.0297 (2) 0.64059 (6) 0.0621 (4)
H3 −0.1976 −0.0190 0.6733 0.075*
C4 −0.3643 (2) 0.0422 (2) 0.60563 (6) 0.0627 (4)
H4 −0.4967 0.0014 0.6147 0.075*
C5 −0.3479 (2) 0.1152 (2) 0.55709 (6) 0.0565 (3)
H5 −0.4698 0.1247 0.5338 0.068*
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)
C9 0.2276 (2) 0.46866 (18) 0.36247 (5) 0.0500 (3)
C10 0.3030 (2) 0.55163 (17) 0.31753 (5) 0.0480 (3)
C11 0.3279 (3) 0.7018 (2) 0.23422 (6) 0.0643 (4)
H11 0.3078 0.7541 0.2016 0.077*
C12 0.5205 (3) 0.6920 (2) 0.26256 (7) 0.0631 (4)
C13 0.5080 (2) 0.60554 (18) 0.31021 (6) 0.0547 (3)
H13 0.6259 0.5869 0.3342 0.066*
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)
N3 0.02776 (18) 0.43483 (15) 0.36467 (4) 0.0530 (3)
S1 0.10458 (5) 0.30465 (5) 0.466131 (13) 0.04910 (12)
S2 0.12673 (6) 0.60757 (5) 0.265024 (14) 0.06061 (14)
H9 0.333 (3) 0.444 (2) 0.3905 (6) 0.065 (4)*
H1 0.158 (3) 0.206 (2) 0.5694 (7) 0.071 (5)*
H12 0.645 (3) 0.736 (3) 0.2497 (8) 0.086 (6)*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
C1 0.0472 (7) 0.0616 (8) 0.0537 (7) −0.0008 (6) 0.0013 (6) −0.0007 (6)
C2 0.0579 (8) 0.0733 (10) 0.0520 (8) 0.0033 (7) −0.0038 (6) 0.0016 (7)
C3 0.0714 (9) 0.0656 (9) 0.0502 (8) 0.0040 (7) 0.0103 (7) 0.0006 (7)
C4 0.0557 (8) 0.0725 (10) 0.0617 (9) −0.0027 (7) 0.0151 (7) −0.0015 (7)
C5 0.0455 (7) 0.0690 (9) 0.0549 (8) 0.0005 (6) 0.0033 (6) −0.0047 (7)
C6 0.0460 (6) 0.0435 (7) 0.0486 (6) 0.0036 (5) 0.0032 (5) −0.0061 (5)
C7 0.0425 (6) 0.0452 (6) 0.0516 (7) 0.0016 (5) 0.0007 (5) −0.0035 (5)
C8 0.0466 (7) 0.0514 (7) 0.0509 (7) 0.0011 (5) −0.0026 (5) 0.0001 (6)
C9 0.0513 (7) 0.0494 (7) 0.0483 (7) 0.0046 (6) −0.0021 (5) −0.0003 (6)
C10 0.0496 (7) 0.0469 (7) 0.0467 (7) 0.0051 (5) −0.0010 (5) −0.0019 (5)
C11 0.0729 (10) 0.0655 (9) 0.0537 (8) −0.0013 (7) 0.0004 (7) 0.0108 (7)
C12 0.0590 (8) 0.0636 (10) 0.0670 (9) −0.0037 (7) 0.0073 (7) 0.0085 (7)
C13 0.0503 (7) 0.0552 (8) 0.0576 (8) 0.0031 (6) −0.0020 (6) 0.0031 (6)
N1 0.0443 (6) 0.0864 (9) 0.0647 (8) −0.0049 (6) −0.0039 (5) 0.0167 (7)
N2 0.0479 (6) 0.0901 (10) 0.0622 (7) −0.0051 (6) −0.0068 (5) 0.0208 (7)
N3 0.0518 (6) 0.0564 (7) 0.0499 (6) −0.0003 (5) −0.0009 (5) 0.0045 (5)
S1 0.04071 (18) 0.0581 (2) 0.04783 (19) 0.00331 (13) −0.00016 (12) 0.00054 (14)
S2 0.0538 (2) 0.0724 (3) 0.0536 (2) −0.00062 (16) −0.00781 (15) 0.00514 (17)
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Geometric parameters (Å, °)

C1—C2 1.381 (2) C8—N3 1.3787 (18)
C1—C6 1.3875 (19) C8—S1 1.7411 (13)
C1—H1 0.923 (18) C9—N3 1.2770 (18)
C2—C3 1.377 (2) C9—C10 1.4335 (19)
C2—H2 0.93 C9—H9 0.952 (16)
C3—C4 1.374 (2) C10—C13 1.3697 (19)
C3—H3 0.93 C10—S2 1.7229 (13)
C4—C5 1.380 (2) C11—C12 1.353 (2)
C4—H4 0.93 C11—S2 1.6993 (17)
C5—C6 1.3900 (19) C11—H11 0.93
C5—H5 0.93 C12—C13 1.403 (2)
C6—C7 1.4684 (19) C12—H12 0.929 (19)
C7—N1 1.3039 (17) C13—H13 0.93
C7—S1 1.7234 (13) N1—N2 1.3696 (19)
C8—N2 1.2987 (18)
C2—C1—C6 120.44 (14) N2—C8—S1 113.44 (11)
C2—C1—H1 121.1 (12) N3—C8—S1 127.22 (10)
C6—C1—H1 118.3 (11) N3—C9—C10 120.78 (12)
C3—C2—C1 120.20 (14) N3—C9—H9 122.7 (10)
C3—C2—H2 119.9 C10—C9—H9 116.5 (10)
C1—C2—H2 119.9 C13—C10—C9 128.09 (12)
C4—C3—C2 119.90 (14) C13—C10—S2 110.88 (10)
C4—C3—H3 120.0 C9—C10—S2 120.94 (10)
C2—C3—H3 120.0 C12—C11—S2 112.30 (12)
C3—C4—C5 120.28 (14) C12—C11—H11 123.9
C3—C4—H4 119.9 S2—C11—H11 123.9
C5—C4—H4 119.9 C11—C12—C13 112.73 (14)
C4—C5—C6 120.40 (14) C11—C12—H12 121.0 (13)
C4—C5—H5 119.8 C13—C12—H12 126.3 (13)
C6—C5—H5 119.8 C10—C13—C12 112.57 (13)
C1—C6—C5 118.77 (13) C10—C13—H13 123.7
C1—C6—C7 121.70 (12) C12—C13—H13 123.7
C5—C6—C7 119.53 (12) C7—N1—N2 113.15 (12)
N1—C7—C6 122.79 (12) C8—N2—N1 112.78 (12)
N1—C7—S1 113.62 (11) C9—N3—C8 120.94 (12)
C6—C7—S1 123.58 (9) C7—S1—C8 87.01 (6)
N2—C8—N3 119.33 (12) C11—S2—C10 91.51 (7)
C6—C1—C2—C3 0.9 (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—C6 0.9 (2) N3—C8—N2—N1 −178.89 (13)
C2—C1—C6—C5 −0.3 (2) S1—C8—N2—N1 0.45 (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—C7 178.55 (14) N2—C8—N3—C9 176.50 (15)
C1—C6—C7—N1 −175.17 (14) S1—C8—N3—C9 −2.7 (2)
C5—C6—C7—N1 5.7 (2) N1—C7—S1—C8 0.32 (12)
C1—C6—C7—S1 6.05 (19) C6—C7—S1—C8 179.20 (12)
C5—C6—C7—S1 −173.02 (11) N2—C8—S1—C7 −0.44 (13)
N3—C9—C10—C13 175.89 (14) N3—C8—S1—C7 178.84 (13)
N3—C9—C10—S2 −0.24 (19) C12—C11—S2—C10 −0.24 (14)
S2—C11—C12—C13 0.5 (2) C13—C10—S2—C11 −0.04 (12)
C9—C10—C13—C12 −176.14 (14) C9—C10—S2—C11 176.70 (12)
S2—C10—C13—C12 0.30 (17)
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Footnotes

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

References

  1. Dege, N. M., Şekerci, M. S., Servi, S. M., Dinçer, M. Ü. & Demirbaş, Ü. (2006). Turk. J. Chem.30, 103–108.
  2. Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  3. Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  4. Foroumadi, A., Mansouri, S., Kiani, Z. & Rahmani, A. (2003). Eur. J. Med. Chem.38, 851–854. [DOI] [PubMed]
  5. Foroumadi, A., Soltani, F., Moshafi, M. H. & Ashraf-Askari, R. (2003). Farmaco, 58, 1023–1028. [DOI] [PubMed]
  6. Genc, M. & Servi, S. (2005). Heteroat. Chem.16, 142–147.
  7. Holla, B. S., Poorjary, K. N., Rao, B. S. & Shivananda, M. K. (2002). Eur. J. Med. Chem.37, 511–517. [DOI] [PubMed]
  8. Servi, S., Genc, M., Gur, S. & Koca, M. (2005). Eur. J. Med. Chem.40, 687–693. [DOI] [PubMed]
  9. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  10. Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
  11. Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

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

e-65-o1668-sup1.cif (16.7KB, cif)

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

e-65-o1668-Isup2.hkl (126KB, hkl)

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

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

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