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accessN,N′-Bis(2-thienylmethylene)benzene-1,4-diamine
aSchool of Pharmaceutical Science, Harbin Medical University, Harbin 150086, People's Republic of China
*Correspondence e-mail: liufengzhi@live.cn
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![[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.]](../../../../../../logos/arrows/e_arr.gif "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.")
); Koizumi et al. (2005); Boskovic et al. (2003); Oshio et al. (2005). For the synthesis, see: Kannappan et al. (2005).
![[Scheme 1]](im2135scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2002); cell SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536809031869/im2135sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809031869/im2135Isup2.hkl
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 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%.
All H atoms were placed in calculated positions with C—H = 0.93Å and refined as riding with Uiso(H) = 1.2Ueq(carrier).
Data collection: APEX2 (Bruker, 2002); cell SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./im2135fig1thm.gif) | 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). |
| C16H12N2S2 | F(000) = 308 |
| Mr = 296.40 | Dx = 1.349 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1252 reflections |
| a = 6.1882 (7) Å | θ = 3.1–25.0° |
| b = 7.2371 (9) Å | µ = 0.36 mm−1 |
| c = 16.375 (2) Å | T = 294 K |
| β = 95.860 (2)° | Block, yellow |
| V = 729.5 (2) Å3 | 0.15 × 0.11 × 0.09 mm |
| Z = 2 |
| Bruker APEXII CCD area-detector diffractometer | 1252 independent reflections |
| Radiation source: fine-focus sealed tube | 1021 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.019 |
| ϕ and ω scans | θmax = 25.0°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −7→7 |
| Tmin = 0.949, Tmax = 0.969 | k = −8→8 |
| 3380 measured reflections | l = −19→10 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.196 | H-atom parameters not refined |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.141P)2 + 0.3146P] where P = (Fo2 + 2Fc2)/3 |
| 1252 reflections | (Δ/σ)max < 0.001 |
| 91 parameters | Δρmax = 1.07 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
| C16H12N2S2 | V = 729.5 (2) Å3 |
| Mr = 296.40 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.1882 (7) Å | µ = 0.36 mm−1 |
| b = 7.2371 (9) Å | T = 294 K |
| c = 16.375 (2) Å | 0.15 × 0.11 × 0.09 mm |
| β = 95.860 (2)° |
| Bruker APEXII CCD area-detector diffractometer | 1252 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1021 reflections with I > 2σ(I) |
| Tmin = 0.949, Tmax = 0.969 | Rint = 0.019 |
| 3380 measured reflections |
| R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
| wR(F2) = 0.196 | H-atom parameters not refined |
| S = 1.00 | Δρmax = 1.07 e Å−3 |
| 1252 reflections | Δρmin = −0.21 e Å−3 |
| 91 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.15131 (14) | −0.10612 (13) | 0.29041 (6) | 0.0619 (5) | |
| N1 | 0.3196 (4) | 0.1917 (4) | 0.41314 (16) | 0.0486 (7) | |
| C1 | 0.0201 (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 | −0.0333 | 0.4061 | 0.068* | |
| C3 | −0.2234 (6) | −0.2258 (5) | 0.3163 (3) | 0.0664 (10) | |
| H3 | −0.3489 | −0.2972 | 0.3136 | 0.080* | |
| C4 | −0.0594 (6) | −0.2534 (6) | 0.2685 (3) | 0.0707 (11) | |
| H4 | −0.0624 | −0.3437 | 0.2280 | 0.085* | |
| C5 | 0.1188 (5) | 0.1553 (4) | 0.41151 (18) | 0.0456 (7) | |
| H5 | 0.0321 | 0.2297 | 0.4411 | 0.055* | |
| C6 | 0.4043 (5) | 0.3492 (4) | 0.45720 (17) | 0.0422 (7) | |
| C7 | 0.3093 (5) | 0.5209 (5) | 0.4490 (2) | 0.0564 (9) | |
| H7 | 0.1820 | 0.5361 | 0.4142 | 0.068* | |
| C8 | 0.6000 (6) | 0.3299 (5) | 0.5086 (2) | 0.0576 (9) | |
| H8 | 0.6681 | 0.2153 | 0.5138 | 0.069* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0552 (6) | 0.0657 (7) | 0.0656 (7) | −0.0030 (4) | 0.0105 (4) | −0.0170 (4) |
| N1 | 0.0464 (15) | 0.0470 (15) | 0.0525 (15) | −0.0058 (11) | 0.0059 (11) | −0.0114 (12) |
| C1 | 0.0453 (16) | 0.0484 (17) | 0.0436 (15) | 0.0007 (12) | −0.0013 (12) | −0.0027 (13) |
| C2 | 0.0483 (18) | 0.062 (2) | 0.059 (2) | −0.0059 (15) | 0.0054 (15) | −0.0085 (16) |
| C3 | 0.0528 (19) | 0.061 (2) | 0.083 (3) | −0.0100 (16) | −0.0059 (18) | −0.0154 (19) |
| C4 | 0.068 (2) | 0.063 (2) | 0.079 (2) | −0.0017 (18) | −0.0038 (19) | −0.0248 (19) |
| C5 | 0.0500 (17) | 0.0447 (16) | 0.0424 (16) | 0.0006 (13) | 0.0052 (13) | −0.0041 (12) |
| C6 | 0.0422 (16) | 0.0427 (15) | 0.0417 (15) | −0.0024 (11) | 0.0046 (12) | −0.0051 (12) |
| C7 | 0.0480 (17) | 0.0531 (19) | 0.065 (2) | 0.0017 (14) | −0.0066 (15) | −0.0032 (16) |
| C8 | 0.055 (2) | 0.0484 (18) | 0.068 (2) | 0.0073 (14) | −0.0004 (16) | −0.0039 (16) |
| S1—C4 | 1.694 (4) | C3—H3 | 0.9300 |
| S1—C1 | 1.719 (3) | C4—H4 | 0.9300 |
| N1—C5 | 1.268 (4) | C5—H5 | 0.9300 |
| N1—C6 | 1.421 (4) | C6—C7 | 1.375 (4) |
| C1—C2 | 1.371 (4) | C6—C8 | 1.410 (4) |
| C1—C5 | 1.449 (4) | C7—C8i | 1.373 (5) |
| C2—C3 | 1.412 (5) | C7—H7 | 0.9300 |
| C2—H2 | 0.9300 | C8—C7i | 1.373 (5) |
| C3—C4 | 1.358 (6) | C8—H8 | 0.9300 |
| C4—S1—C1 | 91.48 (17) | S1—C4—H4 | 123.5 |
| C5—N1—C6 | 119.1 (3) | N1—C5—C1 | 122.0 (3) |
| C2—C1—C5 | 127.8 (3) | N1—C5—H5 | 119.0 |
| C2—C1—S1 | 111.1 (2) | C1—C5—H5 | 119.0 |
| C5—C1—S1 | 121.1 (2) | C7—C6—C8 | 118.8 (3) |
| C1—C2—C3 | 112.6 (3) | C7—C6—N1 | 122.9 (3) |
| C1—C2—H2 | 123.7 | C8—C6—N1 | 118.2 (3) |
| C3—C2—H2 | 123.7 | C8i—C7—C6 | 120.8 (3) |
| C4—C3—C2 | 111.8 (3) | C8i—C7—H7 | 119.6 |
| C4—C3—H3 | 124.1 | C6—C7—H7 | 119.6 |
| C2—C3—H3 | 124.1 | C7i—C8—C6 | 120.4 (3) |
| C3—C4—S1 | 113.0 (3) | C7i—C8—H8 | 119.8 |
| C3—C4—H4 | 123.5 | C6—C8—H8 | 119.8 |
| Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C16H12N2S2 |
| Mr | 296.40 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 294 |
| a, b, c (Å) | 6.1882 (7), 7.2371 (9), 16.375 (2) |
| β (°) | 95.860 (2) |
| V (Å3) | 729.5 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.36 |
| Crystal size (mm) | 0.15 × 0.11 × 0.09 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
| Tmin, Tmax | 0.949, 0.969 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3380, 1252, 1021 |
| Rint | 0.019 |
| (sin θ/λ)max (Å−1) | 0.594 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.196, 1.00 |
| No. of reflections | 1252 |
| No. of parameters | 91 |
| H-atom treatment | H-atom parameters not refined |
| Δρmax, Δρmin (e Å−3) | 1.07, −0.21 |
Computer programs: APEX2 (Bruker, 2002), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge financial support by the Science Foundation of Harbin Medical University.
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. Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
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.