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Acta Crystallogr Sect E Struct Rep Online. Sep 1, 2012; 68(Pt 9): o2673.
Published online Aug 11, 2012. doi:  10.1107/S1600536812033120
PMCID: PMC3435696
(Z)-3-Meth­oxy-N-[(5-nitro­thio­phen-2-yl)methyl­idene]aniline
Tufan Akbal,a* Erbil Ağar,b and Ahmet Erdönmeza
aOndokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey
bOndokuz Mayıs University, Arts and Sciences Faculty, Department of Chemistry, 55139 Samsun, Turkey
Correspondence e-mail: takbal/at/omu.edu.tr
Received June 12, 2012; Accepted July 21, 2012.
Abstract
In the title compound, C12H10N2O3S, the dihedral angle between the benzene and thio­phene rings is 43.17 (4)°. The crystal structure 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 absolute structure 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 Schiff bases, see: Barton & Ollis (1979 [triangle]); Taggi et al. (2002 [triangle]). For a related structure, see: Ceylan et al. (2011 [triangle]).
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Object name is e-68-o2673-scheme1.jpg Object name is e-68-o2673-scheme1.jpg
Crystal data  
  • C12H10N2O3S
  • M r = 262.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2673-efi1.jpg
  • a = 7.4612 (3) Å
  • b = 10.8737 (5) Å
  • c = 14.8465 (9) Å
  • V = 1204.51 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 296 K
  • 0.69 × 0.51 × 0.28 mm
Data collection  
  • Stoe IPDS 2 diffractometer
  • Absorption correction: integration (X-RED; Stoe & Cie, 2002 [triangle]) T min = 0.873, T max = 0.938
  • 5538 measured reflections
  • 2375 independent reflections
  • 2200 reflections with I > 2σ(I)
  • R int = 0.034
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.076
  • S = 1.02
  • 2375 reflections
  • 165 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.18 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 986 Friedel pairs
  • Flack parameter: 0.31 (6)
Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (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 datablock(s) I, global. DOI: 10.1107/S1600536812033120/pv2561sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033120/pv2561Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812033120/pv2561Isup4.mol
Supplementary material file. DOI: 10.1107/S1600536812033120/pv2561Isup4.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the Ondokuz Mayis University Research Fund for financial support of this project.
supplementary crystallographic information
Comment
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.
Experimental
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).
Refinement
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 refinement 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.
Figures
Fig. 1.
Fig. 1.
The molecular structure of title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Fig. 2.
A view of the crystal packing of the title compound. Hydrogen atoms have been excluded for clarity.
Crystal data
C12H10N2O3SF(000) = 544
Mr = 262.29Dx = 1.446 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5538 reflections
a = 7.4612 (3) Åθ = 2.3–26°
b = 10.8737 (5) ŵ = 0.27 mm1
c = 14.8465 (9) ÅT = 296 K
V = 1204.51 (10) Å3Prism, yellow
Z = 40.69 × 0.51 × 0.28 mm
Data collection
Stoe IPDS 2 diffractometer2375 independent reflections
Radiation source: fine-focus sealed tube2200 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
w–scan rotationθmax = 26.0°, θmin = 2.3°
Absorption correction: integration (X-RED; Stoe & Cie, 2002)h = −8→9
Tmin = 0.873, Tmax = 0.938k = −13→13
5538 measured reflectionsl = −15→18
Refinement
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.030w = 1/[σ2(Fo2) + (0.0517P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076(Δ/σ)max = 0.001
S = 1.02Δρmax = 0.17 e Å3
2375 reflectionsΔρmin = −0.18 e Å3
165 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0097 (18)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983),986 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.31 (6)
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
S10.17537 (6)0.72680 (4)0.17461 (3)0.04740 (13)
O30.2561 (2)0.78260 (13)−0.33068 (9)0.0645 (3)
N10.1374 (2)0.81303 (13)−0.01636 (9)0.0475 (3)
N20.1792 (2)0.60779 (17)0.33474 (11)0.0665 (4)
O10.2270 (3)0.70702 (19)0.36455 (10)0.0961 (6)
C10.1284 (2)0.86180 (14)−0.10418 (11)0.0440 (4)
C30.1854 (2)0.85202 (15)−0.26249 (11)0.0479 (4)
C70.1414 (2)0.60021 (16)0.24090 (12)0.0490 (4)
C100.1066 (2)0.64354 (15)0.08297 (11)0.0449 (4)
C40.1172 (3)0.96946 (18)−0.27339 (13)0.0585 (5)
H40.11311.0056−0.33010.070*
C60.0617 (3)0.98144 (16)−0.11459 (13)0.0539 (4)
H60.02241.0258−0.06480.065*
O20.1619 (3)0.51571 (17)0.38055 (10)0.0973 (6)
C80.0809 (3)0.50020 (17)0.19685 (13)0.0560 (5)
H80.05550.42500.22380.067*
C50.0552 (3)1.03209 (18)−0.19860 (14)0.0619 (5)
H50.00791.1106−0.20570.074*
C20.1906 (2)0.79816 (13)−0.17871 (11)0.0442 (3)
H20.23600.7190−0.17210.053*
C110.0970 (2)0.70084 (16)−0.00462 (11)0.0471 (4)
H110.06020.6542−0.05380.057*
C90.0616 (3)0.52531 (17)0.10520 (13)0.0546 (4)
H90.02220.46760.06340.065*
C120.2302 (4)0.8228 (3)−0.42063 (14)0.0905 (8)
H12A0.28640.7659−0.46120.136*
H12B0.28240.9028−0.42810.136*
H12C0.10420.8268−0.43340.136*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
S10.0552 (2)0.0474 (2)0.03953 (19)−0.00386 (17)0.00184 (18)−0.00330 (17)
O30.0855 (9)0.0682 (8)0.0397 (6)0.0033 (7)0.0063 (6)0.0038 (6)
N10.0494 (7)0.0529 (7)0.0401 (7)−0.0007 (6)−0.0015 (6)−0.0038 (6)
N20.0752 (11)0.0795 (10)0.0447 (8)0.0042 (9)0.0000 (9)0.0045 (8)
O10.1360 (17)0.1054 (13)0.0468 (8)−0.0233 (12)−0.0092 (9)−0.0107 (9)
C10.0418 (8)0.0459 (8)0.0444 (9)−0.0028 (7)−0.0040 (7)−0.0006 (7)
C30.0481 (9)0.0512 (8)0.0443 (8)−0.0065 (8)−0.0015 (8)0.0033 (7)
C70.0494 (9)0.0555 (9)0.0421 (8)0.0057 (8)0.0031 (7)0.0042 (7)
C100.0449 (9)0.0496 (8)0.0403 (8)0.0003 (7)0.0005 (7)−0.0045 (7)
C40.0659 (11)0.0538 (9)0.0558 (10)−0.0045 (9)−0.0125 (9)0.0135 (9)
C60.0565 (10)0.0463 (9)0.0590 (11)0.0008 (8)−0.0086 (9)−0.0075 (8)
O20.1395 (16)0.0977 (11)0.0546 (9)0.0113 (13)0.0039 (10)0.0283 (9)
C80.0616 (11)0.0467 (9)0.0598 (11)0.0012 (7)0.0033 (9)0.0068 (8)
C50.0670 (11)0.0445 (9)0.0742 (13)0.0061 (8)−0.0134 (10)0.0034 (9)
C20.0451 (8)0.0418 (7)0.0456 (8)−0.0014 (6)−0.0029 (7)0.0026 (7)
C110.0485 (9)0.0546 (9)0.0382 (8)−0.0010 (7)−0.0002 (7)−0.0056 (7)
C90.0621 (10)0.0482 (9)0.0534 (10)0.0002 (8)−0.0032 (9)−0.0078 (8)
C120.118 (2)0.1166 (19)0.0373 (10)0.0071 (17)0.0024 (12)0.0116 (12)
Geometric parameters (Å, º)
S1—C71.7110 (18)C10—C111.444 (2)
S1—C101.7128 (17)C4—C51.382 (3)
O3—C31.369 (2)C4—H40.9300
O3—C121.418 (3)C6—C51.364 (3)
N1—C111.269 (2)C6—H60.9300
N1—C11.409 (2)C8—C91.395 (3)
N2—O21.217 (2)C8—H80.9300
N2—O11.220 (2)C5—H50.9300
N2—C71.424 (2)C2—H20.9300
C1—C21.385 (2)C11—H110.9300
C1—C61.401 (2)C9—H90.9300
C3—C21.375 (2)C12—H12A0.9600
C3—C41.384 (3)C12—H12B0.9600
C7—C81.347 (3)C12—H12C0.9600
C10—C91.369 (3)
C7—S1—C1089.27 (8)C1—C6—H6120.4
C3—O3—C12118.30 (17)C7—C8—C9110.49 (17)
C11—N1—C1118.54 (14)C7—C8—H8124.8
O2—N2—O1123.77 (18)C9—C8—H8124.8
O2—N2—C7118.57 (18)C6—C5—C4121.58 (17)
O1—N2—C7117.66 (17)C6—C5—H5119.2
C2—C1—C6119.65 (16)C4—C5—H5119.2
C2—C1—N1122.36 (14)C3—C2—C1120.01 (14)
C6—C1—N1117.92 (15)C3—C2—H2120.0
O3—C3—C2115.04 (15)C1—C2—H2120.0
O3—C3—C4124.34 (16)N1—C11—C10121.81 (15)
C2—C3—C4120.60 (16)N1—C11—H11119.1
C8—C7—N2126.02 (17)C10—C11—H11119.1
C8—C7—S1114.83 (13)C10—C9—C8113.18 (17)
N2—C7—S1119.15 (14)C10—C9—H9123.4
C9—C10—C11127.61 (16)C8—C9—H9123.4
C9—C10—S1112.23 (14)O3—C12—H12A109.5
C11—C10—S1120.14 (12)O3—C12—H12B109.5
C5—C4—C3118.92 (17)H12A—C12—H12B109.5
C5—C4—H4120.5O3—C12—H12C109.5
C3—C4—H4120.5H12A—C12—H12C109.5
C5—C6—C1119.22 (18)H12B—C12—H12C109.5
C5—C6—H6120.4
C11—N1—C1—C2−42.6 (2)N1—C1—C6—C5178.55 (16)
C11—N1—C1—C6140.62 (16)N2—C7—C8—C9−179.03 (19)
C12—O3—C3—C2170.13 (19)S1—C7—C8—C90.5 (2)
C12—O3—C3—C4−11.7 (3)C1—C6—C5—C4−1.7 (3)
O2—N2—C7—C82.6 (3)C3—C4—C5—C60.8 (3)
O1—N2—C7—C8−177.3 (2)O3—C3—C2—C1177.79 (15)
O2—N2—C7—S1−176.88 (17)C4—C3—C2—C1−0.4 (3)
O1—N2—C7—S13.2 (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—N2179.32 (16)C1—N1—C11—C10178.65 (15)
C7—S1—C10—C9−0.11 (15)C9—C10—C11—N1177.72 (17)
C7—S1—C10—C11178.33 (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—C50.3 (3)S1—C10—C9—C80.4 (2)
C2—C1—C6—C51.6 (3)C7—C8—C9—C10−0.5 (2)
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2561).
  • Barton, D. & Ollis, W. D. (1979). Comprehensive Organic Chemistry, Vol 2. Oxford: Pergamon.
  • Ceylan, Ü., Tanak, H., Gümüş, S. & Ağar, E. (2011). Acta Cryst. E67, o2004. [PMC free article] [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst D65, 148–155. [PMC free article] [PubMed]
  • Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.
  • Taggi, A. E., Hafez, A. M., Wack, H., Young, B., Ferraris, D. & Lectka, T. (2002). J. Am. Chem. Soc. 124, 6626–6635. [PubMed]
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