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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2190.
Published online 2009 August 19. doi:  10.1107/S1600536809031869
PMCID: PMC2970153

N,N′-Bis(2-thienylmethyl­ene)benzene-1,4-diamine

Abstract

The Schiff base, C16H12N2S2, has been synthesized by refluxing an ethano­lic solution of thio­phene-2-carbaldehyde and benzene-1,4-diamine. The center of the benzene ring is located on a crystallographic center of inversion. The dihedral angle between the benzene and thio­phene rings is 63.6 (1)°.

Related literature

For general background to Schiff base complexes, see: Andersen et al. (2005 [triangle]); Koizumi et al. (2005 [triangle]); Boskovic et al. (2003 [triangle]); Oshio et al. (2005 [triangle]). For the synthesis, see: Kannappan et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2190-scheme1.jpg

Experimental

Crystal data

  • C16H12N2S2
  • M r = 296.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2190-efi1.jpg
  • a = 6.1882 (7) Å
  • b = 7.2371 (9) Å
  • c = 16.375 (2) Å
  • β = 95.860 (2)°
  • V = 729.5 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.36 mm−1
  • T = 294 K
  • 0.15 × 0.11 × 0.09 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.949, T max = 0.969
  • 3380 measured reflections
  • 1252 independent reflections
  • 1021 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065
  • wR(F 2) = 0.196
  • S = 1.00
  • 1252 reflections
  • 91 parameters
  • H-atom parameters not refined
  • Δρmax = 1.07 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2002 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031869/im2135sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031869/im2135Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support by the Science Foundation of Harbin Medical University.

supplementary crystallographic information

Comment

During the past decades, Schiff bases have been intensively investigated not only because of their strong coordination capability but also due to diverse biological activities, such as e.g. antibacterial and antitumor activities (Andersen et al., 2005; Koizumi et al., 2005; Boskovic et al., 2003; Oshio et al., 2005). Here we report the structure of N,N'-bis-thiophene-2-yl-methylene-1,4-benzenediamine, which could be used as another Schiff base ligand in combination with metal ions.

The molecular structure of the title compound is depicted in Figure 1. The center of the phenyl ring represents a crystallographic center of inversion. The dihedral angle between the phenyl and thiophene rings is 63.6 (1)°. As it is expected the thiophene rings also are perfectly planar with a deviation of the S atom of 0.001 Å.

Experimental

N,N'-Bis-thiophene-2-yl-methylene-1,4-benzenediamine was prepared according to the method reported in the literature (Kannappan et al., 2005). Thiophene-2-carboxaldehyde (0.02 mol) was added to a stirred ethanolic solution of p-phenylenediamine (0.01 mol). The reaction mixture was stirred about 3 h and then the mixture was allowed to stand at room temperature for about two days. Yellow crystals suitable for X-ray diffraction analysis were collected with a yield of 60%. Anal. Calc. for C16H12N2S2: C 64.78, H 4.05, N 9.45%; Found: C 64.59, H 4.01, N 9.25%.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93Å and refined as riding with Uiso(H) = 1.2Ueq(carrier).

Figures

Fig. 1.
View of the molecular structure of the title compound, showing the atomic numbering scheme and 50% probability displacement ellipsoids. Atoms labeled with A at the symmetry positions (-x + 1,-y + 1,-z + 1).

Crystal data

C16H12N2S2F(000) = 308
Mr = 296.40Dx = 1.349 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1252 reflections
a = 6.1882 (7) Åθ = 3.1–25.0°
b = 7.2371 (9) ŵ = 0.36 mm1
c = 16.375 (2) ÅT = 294 K
β = 95.860 (2)°Block, yellow
V = 729.5 (2) Å30.15 × 0.11 × 0.09 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer1252 independent reflections
Radiation source: fine-focus sealed tube1021 reflections with I > 2σ(I)
graphiteRint = 0.019
[var phi] and ω scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)h = −7→7
Tmin = 0.949, Tmax = 0.969k = −8→8
3380 measured reflectionsl = −19→10

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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.196H-atom parameters not refined
S = 1.00w = 1/[σ2(Fo2) + (0.141P)2 + 0.3146P] where P = (Fo2 + 2Fc2)/3
1252 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 1.07 e Å3
0 restraintsΔρmin = −0.21 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
S10.15131 (14)−0.10612 (13)0.29041 (6)0.0619 (5)
N10.3196 (4)0.1917 (4)0.41314 (16)0.0486 (7)
C10.0201 (5)0.0013 (4)0.36497 (18)0.0462 (7)
C2−0.1804 (5)−0.0755 (5)0.3705 (2)0.0565 (9)
H2−0.2774−0.03330.40610.068*
C3−0.2234 (6)−0.2258 (5)0.3163 (3)0.0664 (10)
H3−0.3489−0.29720.31360.080*
C4−0.0594 (6)−0.2534 (6)0.2685 (3)0.0707 (11)
H4−0.0624−0.34370.22800.085*
C50.1188 (5)0.1553 (4)0.41151 (18)0.0456 (7)
H50.03210.22970.44110.055*
C60.4043 (5)0.3492 (4)0.45720 (17)0.0422 (7)
C70.3093 (5)0.5209 (5)0.4490 (2)0.0564 (9)
H70.18200.53610.41420.068*
C80.6000 (6)0.3299 (5)0.5086 (2)0.0576 (9)
H80.66810.21530.51380.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0552 (6)0.0657 (7)0.0656 (7)−0.0030 (4)0.0105 (4)−0.0170 (4)
N10.0464 (15)0.0470 (15)0.0525 (15)−0.0058 (11)0.0059 (11)−0.0114 (12)
C10.0453 (16)0.0484 (17)0.0436 (15)0.0007 (12)−0.0013 (12)−0.0027 (13)
C20.0483 (18)0.062 (2)0.059 (2)−0.0059 (15)0.0054 (15)−0.0085 (16)
C30.0528 (19)0.061 (2)0.083 (3)−0.0100 (16)−0.0059 (18)−0.0154 (19)
C40.068 (2)0.063 (2)0.079 (2)−0.0017 (18)−0.0038 (19)−0.0248 (19)
C50.0500 (17)0.0447 (16)0.0424 (16)0.0006 (13)0.0052 (13)−0.0041 (12)
C60.0422 (16)0.0427 (15)0.0417 (15)−0.0024 (11)0.0046 (12)−0.0051 (12)
C70.0480 (17)0.0531 (19)0.065 (2)0.0017 (14)−0.0066 (15)−0.0032 (16)
C80.055 (2)0.0484 (18)0.068 (2)0.0073 (14)−0.0004 (16)−0.0039 (16)

Geometric parameters (Å, °)

S1—C41.694 (4)C3—H30.9300
S1—C11.719 (3)C4—H40.9300
N1—C51.268 (4)C5—H50.9300
N1—C61.421 (4)C6—C71.375 (4)
C1—C21.371 (4)C6—C81.410 (4)
C1—C51.449 (4)C7—C8i1.373 (5)
C2—C31.412 (5)C7—H70.9300
C2—H20.9300C8—C7i1.373 (5)
C3—C41.358 (6)C8—H80.9300
C4—S1—C191.48 (17)S1—C4—H4123.5
C5—N1—C6119.1 (3)N1—C5—C1122.0 (3)
C2—C1—C5127.8 (3)N1—C5—H5119.0
C2—C1—S1111.1 (2)C1—C5—H5119.0
C5—C1—S1121.1 (2)C7—C6—C8118.8 (3)
C1—C2—C3112.6 (3)C7—C6—N1122.9 (3)
C1—C2—H2123.7C8—C6—N1118.2 (3)
C3—C2—H2123.7C8i—C7—C6120.8 (3)
C4—C3—C2111.8 (3)C8i—C7—H7119.6
C4—C3—H3124.1C6—C7—H7119.6
C2—C3—H3124.1C7i—C8—C6120.4 (3)
C3—C4—S1113.0 (3)C7i—C8—H8119.8
C3—C4—H4123.5C6—C8—H8119.8

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2135).

References

  • Andersen, L. H., Nielsen, I. B., Kristensen, M. B., El Ghazaly, M. O. A., Haacke, S., Nielsen, M. B. & Petersen, M. Å ;. (2005). J. Am. Chem. Soc.127, 12347–12350. [PubMed]
  • Boskovic, C., Bircher, R., Tregenna-Piggott, P. L. W., Güdel, H. U., Paulsen, C., Wernsdorfer, W., Barra, A. L., Khatsko, E., Neels, A. & Stoeckli-Evans, H. (2003). J. Am. Chem. Soc.125, 14046–14058. [PubMed]
  • Bruker (2002). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kannappan, R., Tanase, S., Mutikainen, I., Turpeinen, U. & Reedijk, J. (2005). Inorg. Chim. Acta, 358, 383–388.
  • Koizumi, S., Nihei, M., Nakano, M. & Oshio, H. (2005). Inorg. Chem.44, 1208–1210. [PubMed]
  • Oshio, H., Nihei, M., Koizumi, S., Shiga, T., Nojiri, H., Nakano, M., Shirakawa, N. & Akatsu, M. (2005). J. Am. Chem. Soc.127, 4568–4569. [PubMed]
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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