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access(Z)-3-Methoxy-N-[(5-nitrothiophen-2-yl)methylidene]aniline
aOndokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey, and bOndokuz Mayıs University, Arts and Sciences Faculty, Department of Chemistry, 55139 Samsun, Turkey
*Correspondence e-mail: takbal@omu.edu.tr
In the title compound, C12H10N2O3S, the dihedral angle between the benzene and thiophene rings is 43.17 (4)°. The is devoid of any hydrogen-bonding interactions. However, π–π interactions between the benzene and thiophene rings [distance between ring centroids = 3.6850 (11) Å] stack the molecules along the a axis. The could not be determined as the crystal studied was a racemic twin with a BASF parameter of 0.31 (6).
Related literature
For biological and industrial properties of see: Barton & Ollis (1979![[Barton, D. & Ollis, W. D. (1979). Comprehensive Organic Chemistry, Vol 2. Oxford: Pergamon.]](../../../../../../logos/arrows/e_arr.gif "Barton, D. & Ollis, W. D. (1979). Comprehensive Organic Chemistry, Vol 2. Oxford: Pergamon.")
); Taggi et al. (2002). For a related structure, see: Ceylan et al. (2011).
![[Scheme 1]](pv2561scheme1.gif)
Experimental
Crystal data
|
Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA; data reduction: X-RED32 (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).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536812033120/pv2561sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536812033120/pv2561Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812033120/pv2561Isup4.mol
Supporting information file. DOI: 10.1107/S1600536812033120/pv2561Isup4.cml
The compound title compound was prepared by refluxing a mixture of a solution of 5-nitro-2-thiophene-carboxaldehyde (0.018 g, 0.120 mmol) in ethanol (20 ml) and a solution of 3-methoxyaniline (0.0142 g, 0.120 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. The crystals of the title compound suitable for X-ray analysis were obtained from ethanol by slow evaporation (yield %61; m.p 385–386 K).
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 and 0.96 Å, for aryl and methyl H-atoms, respectively. The Uiso(H) were allowed at 1.5Ueq(C methyl) or 1.2Ueq(C aryl). The compound crystallized as a racemic twin as indicated by SHELXL97 (Sheldrick, 2008). A twin using the commands TWIN and BASF gave a twin fraction of 0.31 (6)/0.69 (6); 986 Friedel pairs of reflections were not merged.
Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (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).
| Fig. 1. The molecular structure of title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Fig. 2. A view of the crystal packing of the title compound. Hydrogen atoms have been excluded for clarity. |
| C12H10N2O3S | F(000) = 544 |
| Mr = 262.29 | Dx = 1.446 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 5538 reflections |
| a = 7.4612 (3) Å | θ = 2.3–26° |
| b = 10.8737 (5) Å | µ = 0.27 mm−1 |
| c = 14.8465 (9) Å | T = 296 K |
| V = 1204.51 (10) Å3 | Prism, yellow |
| Z = 4 | 0.69 × 0.51 × 0.28 mm |
| Stoe IPDS 2 diffractometer | 2375 independent reflections |
| Radiation source: fine-focus sealed tube | 2200 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.034 |
| w–scan rotation | θmax = 26.0°, θmin = 2.3° |
| Absorption correction: integration (X-RED; Stoe & Cie, 2002) | h = −8→9 |
| Tmin = 0.873, Tmax = 0.938 | k = −13→13 |
| 5538 measured reflections | l = −15→18 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.0517P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.076 | (Δ/σ)max = 0.001 |
| S = 1.02 | Δρmax = 0.17 e Å−3 |
| 2375 reflections | Δρmin = −0.18 e Å−3 |
| 165 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0097 (18) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983),986 Friedel pairs |
| Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.31 (6) |
| C12H10N2O3S | V = 1204.51 (10) Å3 |
| Mr = 262.29 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 7.4612 (3) Å | µ = 0.27 mm−1 |
| b = 10.8737 (5) Å | T = 296 K |
| c = 14.8465 (9) Å | 0.69 × 0.51 × 0.28 mm |
| Stoe IPDS 2 diffractometer | 2375 independent reflections |
| Absorption correction: integration (X-RED; Stoe & Cie, 2002) | 2200 reflections with I > 2σ(I) |
| Tmin = 0.873, Tmax = 0.938 | Rint = 0.034 |
| 5538 measured reflections |
| R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.076 | Δρmax = 0.17 e Å−3 |
| S = 1.02 | Δρmin = −0.18 e Å−3 |
| 2375 reflections | Absolute structure: Flack (1983),986 Friedel pairs |
| 165 parameters | Absolute structure parameter: 0.31 (6) |
| 0 restraints |
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 | 0.17537 (6) | 0.72680 (4) | 0.17461 (3) | 0.04740 (13) | |
| O3 | 0.2561 (2) | 0.78260 (13) | −0.33068 (9) | 0.0645 (3) | |
| N1 | 0.1374 (2) | 0.81303 (13) | −0.01636 (9) | 0.0475 (3) | |
| N2 | 0.1792 (2) | 0.60779 (17) | 0.33474 (11) | 0.0665 (4) | |
| O1 | 0.2270 (3) | 0.70702 (19) | 0.36455 (10) | 0.0961 (6) | |
| C1 | 0.1284 (2) | 0.86180 (14) | −0.10418 (11) | 0.0440 (4) | |
| C3 | 0.1854 (2) | 0.85202 (15) | −0.26249 (11) | 0.0479 (4) | |
| C7 | 0.1414 (2) | 0.60021 (16) | 0.24090 (12) | 0.0490 (4) | |
| C10 | 0.1066 (2) | 0.64354 (15) | 0.08297 (11) | 0.0449 (4) | |
| C4 | 0.1172 (3) | 0.96946 (18) | −0.27339 (13) | 0.0585 (5) | |
| H4 | 0.1131 | 1.0056 | −0.3301 | 0.070* | |
| C6 | 0.0617 (3) | 0.98144 (16) | −0.11459 (13) | 0.0539 (4) | |
| H6 | 0.0224 | 1.0258 | −0.0648 | 0.065* | |
| O2 | 0.1619 (3) | 0.51571 (17) | 0.38055 (10) | 0.0973 (6) | |
| C8 | 0.0809 (3) | 0.50020 (17) | 0.19685 (13) | 0.0560 (5) | |
| H8 | 0.0555 | 0.4250 | 0.2238 | 0.067* | |
| C5 | 0.0552 (3) | 1.03209 (18) | −0.19860 (14) | 0.0619 (5) | |
| H5 | 0.0079 | 1.1106 | −0.2057 | 0.074* | |
| C2 | 0.1906 (2) | 0.79816 (13) | −0.17871 (11) | 0.0442 (3) | |
| H2 | 0.2360 | 0.7190 | −0.1721 | 0.053* | |
| C11 | 0.0970 (2) | 0.70084 (16) | −0.00462 (11) | 0.0471 (4) | |
| H11 | 0.0602 | 0.6542 | −0.0538 | 0.057* | |
| C9 | 0.0616 (3) | 0.52531 (17) | 0.10520 (13) | 0.0546 (4) | |
| H9 | 0.0222 | 0.4676 | 0.0634 | 0.065* | |
| C12 | 0.2302 (4) | 0.8228 (3) | −0.42063 (14) | 0.0905 (8) | |
| H12A | 0.2864 | 0.7659 | −0.4612 | 0.136* | |
| H12B | 0.2824 | 0.9028 | −0.4281 | 0.136* | |
| H12C | 0.1042 | 0.8268 | −0.4334 | 0.136* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0552 (2) | 0.0474 (2) | 0.03953 (19) | −0.00386 (17) | 0.00184 (18) | −0.00330 (17) |
| O3 | 0.0855 (9) | 0.0682 (8) | 0.0397 (6) | 0.0033 (7) | 0.0063 (6) | 0.0038 (6) |
| N1 | 0.0494 (7) | 0.0529 (7) | 0.0401 (7) | −0.0007 (6) | −0.0015 (6) | −0.0038 (6) |
| N2 | 0.0752 (11) | 0.0795 (10) | 0.0447 (8) | 0.0042 (9) | 0.0000 (9) | 0.0045 (8) |
| O1 | 0.1360 (17) | 0.1054 (13) | 0.0468 (8) | −0.0233 (12) | −0.0092 (9) | −0.0107 (9) |
| C1 | 0.0418 (8) | 0.0459 (8) | 0.0444 (9) | −0.0028 (7) | −0.0040 (7) | −0.0006 (7) |
| C3 | 0.0481 (9) | 0.0512 (8) | 0.0443 (8) | −0.0065 (8) | −0.0015 (8) | 0.0033 (7) |
| C7 | 0.0494 (9) | 0.0555 (9) | 0.0421 (8) | 0.0057 (8) | 0.0031 (7) | 0.0042 (7) |
| C10 | 0.0449 (9) | 0.0496 (8) | 0.0403 (8) | 0.0003 (7) | 0.0005 (7) | −0.0045 (7) |
| C4 | 0.0659 (11) | 0.0538 (9) | 0.0558 (10) | −0.0045 (9) | −0.0125 (9) | 0.0135 (9) |
| C6 | 0.0565 (10) | 0.0463 (9) | 0.0590 (11) | 0.0008 (8) | −0.0086 (9) | −0.0075 (8) |
| O2 | 0.1395 (16) | 0.0977 (11) | 0.0546 (9) | 0.0113 (13) | 0.0039 (10) | 0.0283 (9) |
| C8 | 0.0616 (11) | 0.0467 (9) | 0.0598 (11) | 0.0012 (7) | 0.0033 (9) | 0.0068 (8) |
| C5 | 0.0670 (11) | 0.0445 (9) | 0.0742 (13) | 0.0061 (8) | −0.0134 (10) | 0.0034 (9) |
| C2 | 0.0451 (8) | 0.0418 (7) | 0.0456 (8) | −0.0014 (6) | −0.0029 (7) | 0.0026 (7) |
| C11 | 0.0485 (9) | 0.0546 (9) | 0.0382 (8) | −0.0010 (7) | −0.0002 (7) | −0.0056 (7) |
| C9 | 0.0621 (10) | 0.0482 (9) | 0.0534 (10) | 0.0002 (8) | −0.0032 (9) | −0.0078 (8) |
| C12 | 0.118 (2) | 0.1166 (19) | 0.0373 (10) | 0.0071 (17) | 0.0024 (12) | 0.0116 (12) |
| S1—C7 | 1.7110 (18) | C10—C11 | 1.444 (2) |
| S1—C10 | 1.7128 (17) | C4—C5 | 1.382 (3) |
| O3—C3 | 1.369 (2) | C4—H4 | 0.9300 |
| O3—C12 | 1.418 (3) | C6—C5 | 1.364 (3) |
| N1—C11 | 1.269 (2) | C6—H6 | 0.9300 |
| N1—C1 | 1.409 (2) | C8—C9 | 1.395 (3) |
| N2—O2 | 1.217 (2) | C8—H8 | 0.9300 |
| N2—O1 | 1.220 (2) | C5—H5 | 0.9300 |
| N2—C7 | 1.424 (2) | C2—H2 | 0.9300 |
| C1—C2 | 1.385 (2) | C11—H11 | 0.9300 |
| C1—C6 | 1.401 (2) | C9—H9 | 0.9300 |
| C3—C2 | 1.375 (2) | C12—H12A | 0.9600 |
| C3—C4 | 1.384 (3) | C12—H12B | 0.9600 |
| C7—C8 | 1.347 (3) | C12—H12C | 0.9600 |
| C10—C9 | 1.369 (3) | ||
| C7—S1—C10 | 89.27 (8) | C1—C6—H6 | 120.4 |
| C3—O3—C12 | 118.30 (17) | C7—C8—C9 | 110.49 (17) |
| C11—N1—C1 | 118.54 (14) | C7—C8—H8 | 124.8 |
| O2—N2—O1 | 123.77 (18) | C9—C8—H8 | 124.8 |
| O2—N2—C7 | 118.57 (18) | C6—C5—C4 | 121.58 (17) |
| O1—N2—C7 | 117.66 (17) | C6—C5—H5 | 119.2 |
| C2—C1—C6 | 119.65 (16) | C4—C5—H5 | 119.2 |
| C2—C1—N1 | 122.36 (14) | C3—C2—C1 | 120.01 (14) |
| C6—C1—N1 | 117.92 (15) | C3—C2—H2 | 120.0 |
| O3—C3—C2 | 115.04 (15) | C1—C2—H2 | 120.0 |
| O3—C3—C4 | 124.34 (16) | N1—C11—C10 | 121.81 (15) |
| C2—C3—C4 | 120.60 (16) | N1—C11—H11 | 119.1 |
| C8—C7—N2 | 126.02 (17) | C10—C11—H11 | 119.1 |
| C8—C7—S1 | 114.83 (13) | C10—C9—C8 | 113.18 (17) |
| N2—C7—S1 | 119.15 (14) | C10—C9—H9 | 123.4 |
| C9—C10—C11 | 127.61 (16) | C8—C9—H9 | 123.4 |
| C9—C10—S1 | 112.23 (14) | O3—C12—H12A | 109.5 |
| C11—C10—S1 | 120.14 (12) | O3—C12—H12B | 109.5 |
| C5—C4—C3 | 118.92 (17) | H12A—C12—H12B | 109.5 |
| C5—C4—H4 | 120.5 | O3—C12—H12C | 109.5 |
| C3—C4—H4 | 120.5 | H12A—C12—H12C | 109.5 |
| C5—C6—C1 | 119.22 (18) | H12B—C12—H12C | 109.5 |
| C5—C6—H6 | 120.4 | ||
| C11—N1—C1—C2 | −42.6 (2) | N1—C1—C6—C5 | 178.55 (16) |
| C11—N1—C1—C6 | 140.62 (16) | N2—C7—C8—C9 | −179.03 (19) |
| C12—O3—C3—C2 | 170.13 (19) | S1—C7—C8—C9 | 0.5 (2) |
| C12—O3—C3—C4 | −11.7 (3) | C1—C6—C5—C4 | −1.7 (3) |
| O2—N2—C7—C8 | 2.6 (3) | C3—C4—C5—C6 | 0.8 (3) |
| O1—N2—C7—C8 | −177.3 (2) | O3—C3—C2—C1 | 177.79 (15) |
| O2—N2—C7—S1 | −176.88 (17) | C4—C3—C2—C1 | −0.4 (3) |
| O1—N2—C7—S1 | 3.2 (3) | C6—C1—C2—C3 | −0.6 (2) |
| C10—S1—C7—C8 | −0.21 (15) | N1—C1—C2—C3 | −177.34 (15) |
| C10—S1—C7—N2 | 179.32 (16) | C1—N1—C11—C10 | 178.65 (15) |
| C7—S1—C10—C9 | −0.11 (15) | C9—C10—C11—N1 | 177.72 (17) |
| C7—S1—C10—C11 | 178.33 (15) | S1—C10—C11—N1 | −0.5 (2) |
| O3—C3—C4—C5 | −177.69 (18) | C11—C10—C9—C8 | −177.90 (17) |
| C2—C3—C4—C5 | 0.3 (3) | S1—C10—C9—C8 | 0.4 (2) |
| C2—C1—C6—C5 | 1.6 (3) | C7—C8—C9—C10 | −0.5 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C12H10N2O3S |
| Mr | 262.29 |
| Crystal system, space group | Orthorhombic, P212121 |
| Temperature (K) | 296 |
| a, b, c (Å) | 7.4612 (3), 10.8737 (5), 14.8465 (9) |
| V (Å3) | 1204.51 (10) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.27 |
| Crystal size (mm) | 0.69 × 0.51 × 0.28 |
| Data collection | |
| Diffractometer | Stoe IPDS 2 diffractometer |
| Absorption correction | Integration (X-RED; Stoe & Cie, 2002) |
| Tmin, Tmax | 0.873, 0.938 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5538, 2375, 2200 |
| Rint | 0.034 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.076, 1.02 |
| No. of reflections | 2375 |
| No. of parameters | 165 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
| Absolute structure | Flack (1983),986 Friedel pairs |
| Absolute structure parameter | 0.31 (6) |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Acknowledgements
The authors thank the Ondokuz Mayis University Research Fund for financial support of this project.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Schiff bases are used as starting materials in the synthesis of important drugs, such as antibiotics and antiallergic, antiphlogistic, and antitumor substances (Barton & Ollis, 1979). In addition, they have a wide range of industrial applications, such as dyes and pigments (Taggi et al., 2002). Herein we report the synthesis and crystal structure of the title compound.
In the title compound (Fig. 1), the dihedral angle between the nitro-thiophene (C7—C10/S1) and the benzene ring (Cl—C6) is 47.14 (4) °. The bond distances and angles in the title compound agree very well with the corresponding bond distances and angles reported in a closely related compound (Ceylan et al. 2011). The structure is devoid of any hydrogen bonding interactions. However, π—π interactions between the centroids of the benzene and thiophene rings (distance between ring centroids = 3.6850 (11) Å) are observed in the crystal structure.