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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2087.
Published online 2008 October 9. doi:  10.1107/S1600536808032042
PMCID: PMC2959688

3,4-Dimeth­oxy-N-(4-nitro­benzyl­idene)­aniline

Abstract

In the title mol­ecule, C15H14N2O4, the dihedral angle between the two benzene rings is 29.52 (8)°. The nitro and two meth­oxy substituents are almost coplanar with their respective benzene rings. The crystal structure is stabilized by inter­molecular C—H(...)O inter­actions.

Related literature

For general background, see: Bey & Vevert (1977 [triangle]); Bezas & Zervas (1961 [triangle]); Fleet & Fleming (1969 [triangle]); Lucas et al. (1960 [triangle]); Macho et al. (2004 [triangle]). For a related structure, see: Akkurt et al. (2005 [triangle]).

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Object name is e-64-o2087-scheme1.jpg

Experimental

Crystal data

  • C15H14N2O4
  • M r = 286.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2087-efi1.jpg
  • a = 7.9536 (4) Å
  • b = 8.2258 (3) Å
  • c = 21.3418 (10) Å
  • β = 96.125 (4)°
  • V = 1388.31 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 296 K
  • 0.25 × 0.21 × 0.18 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.975, T max = 0.982
  • 14598 measured reflections
  • 2880 independent reflections
  • 1797 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.120
  • S = 0.83
  • 2880 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.13 e Å−3
  • Δρmin = −0.12 e Å−3

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 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032042/tk2312sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808032042/tk2312Isup2.hkl

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

Comment

Schiff bases belong to a widely used group of organic intermediates which are important for production of certain chemicals, such as pharmaceuticals and rubber additives (Macho et al., 2004), and as amino protective groups in organic synthesis (Bey & Vevert, 1977; Lucas et al., 1960; Fleet & Fleming, 1969; Bezas & Zervas, 1961). As we are interested in Schiff bases, we report here the crystal structure of the title compound, (I).

In (I), Fig. 1, the dihedral angle between the two benzene rings (C1–C6) and (C10–C15) is 29.52 (8)° and the C1—N1—C9—C10 torsion angle is 176.12 (15)°. The nitro and two methoxy substituents are coplanar with their respective benzene rings.

The crystal structure of (I) is stabilized by intermolecular C—H···O interactions, Fig. 2 and Table 1.

Experimental

A mixture of 3,4-dimethoxyaniline (3 mmol) and 4-nitrobenzaldehyde (3 mmol) was refluxed in EtOH for 4 h. After cooling the solution, the formed precipitate was filtered off and washed with ethanol to give pure Schiff base as an orange solid in an 89% yield; m. pt. = 429–431 K. IR (KBr, cm-1): 1600.3 (C?N). 1H NMR (CDCl3) δ 3.92, 3.94 (2 x OCH3, s, 6H), 6.92–8.66 (ArH, m, 7H), 8.90 (HC?N, s, 1H). 13C NMR (CDCl3) δ 55.97, 56.12 (2 OCH3), 105.63–149.50 (C?C aromatic carbons), 155.03 (C?N).

Refinement

After checking for their presence in the Fourier map, all hydrogen atoms were placed in calculated positions and allowed to ride on their parent atoms with the C—H = 0.93 Å (aromatic) and C—H = 0.96 Å (methy) with Uiso(H) = 1.2Ueq(Caromatic) and 1.5Ueq(Cmethyl).

Figures

Fig. 1.
View of (I) showing with the atom-numbering scheme and 50% probability displacement ellipsoids
Fig. 2.
View down the b axis of the packing and C—H···O contacts in the unit cell of (I). H atoms not involved in C—H···O contacts (dashed lines) have been omitted for clarity.

Crystal data

C15H14N2O4F(000) = 600
Mr = 286.28Dx = 1.370 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 11667 reflections
a = 7.9536 (4) Åθ = 1.9–27.3°
b = 8.2258 (3) ŵ = 0.10 mm1
c = 21.3418 (10) ÅT = 296 K
β = 96.125 (4)°Prism, brown
V = 1388.31 (11) Å30.25 × 0.21 × 0.18 mm
Z = 4

Data collection

Stoe IPDS II diffractometer2880 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus1797 reflections with I > 2σ(I)
plane graphiteRint = 0.038
Detector resolution: 6.67 pixels mm-1θmax = 26.5°, θmin = 1.9°
ω scansh = −9→9
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −10→10
Tmin = 0.975, Tmax = 0.982l = −26→26
14598 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.120w = 1/[σ2(Fo2) + (0.0824P)2] where P = (Fo2 + 2Fc2)/3
S = 0.83(Δ/σ)max < 0.001
2880 reflectionsΔρmax = 0.13 e Å3
191 parametersΔρmin = −0.12 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=KFc[1+0.001Fc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0071 (16)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
O10.34730 (16)−0.17529 (15)0.28084 (6)0.0633 (4)
O20.14131 (16)0.04285 (15)0.23416 (6)0.0624 (4)
O30.1545 (2)1.09341 (17)0.58860 (7)0.0859 (6)
O40.2133 (2)0.96182 (16)0.67456 (6)0.0775 (6)
N10.2395 (2)0.38177 (18)0.41916 (7)0.0580 (5)
N20.1851 (2)0.96644 (18)0.61754 (7)0.0578 (5)
C10.2679 (2)0.2324 (2)0.38839 (8)0.0524 (6)
C20.3732 (2)0.1113 (2)0.41434 (8)0.0581 (6)
C30.4020 (2)−0.0275 (2)0.37992 (9)0.0575 (6)
C40.3240 (2)−0.0470 (2)0.31966 (8)0.0509 (5)
C50.2137 (2)0.0741 (2)0.29350 (8)0.0503 (6)
C60.1891 (2)0.2128 (2)0.32730 (8)0.0536 (6)
C70.4578 (3)−0.3022 (3)0.30482 (11)0.0780 (8)
C80.0173 (3)0.1542 (2)0.20751 (9)0.0637 (7)
C90.2415 (2)0.3850 (2)0.47827 (9)0.0571 (6)
C100.2237 (2)0.5361 (2)0.51351 (8)0.0520 (6)
C110.1908 (2)0.6842 (2)0.48291 (8)0.0574 (6)
C120.1756 (2)0.8243 (2)0.51682 (8)0.0566 (6)
C130.1945 (2)0.8156 (2)0.58166 (8)0.0492 (5)
C140.2255 (2)0.6721 (2)0.61381 (8)0.0560 (6)
C150.2377 (2)0.5328 (2)0.57890 (8)0.0588 (6)
H20.425400.122600.455200.0700*
H30.47450−0.107700.397700.0690*
H60.119000.294500.309200.0640*
H7A0.46300−0.384300.273100.1170*
H7B0.41610−0.349200.341300.1170*
H7C0.56890−0.258700.316200.1170*
H8A−0.024200.119300.165800.0960*
H8B0.066800.260300.205500.0960*
H8C−0.074700.158400.233200.0960*
H90.254800.287700.500500.0690*
H110.179100.688100.439100.0690*
H120.152900.923000.496400.0680*
H140.237700.669200.657600.0670*
H150.255700.433800.599600.0710*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0634 (8)0.0591 (7)0.0660 (8)0.0120 (6)0.0008 (6)−0.0126 (6)
O20.0720 (8)0.0637 (8)0.0490 (7)0.0131 (6)−0.0053 (6)−0.0096 (6)
O30.1359 (14)0.0530 (8)0.0664 (9)0.0118 (8)−0.0004 (9)0.0023 (7)
O40.1171 (12)0.0690 (9)0.0466 (8)−0.0019 (8)0.0094 (8)−0.0067 (7)
N10.0677 (10)0.0568 (9)0.0489 (9)−0.0007 (7)0.0037 (7)−0.0073 (7)
N20.0698 (10)0.0533 (9)0.0501 (9)−0.0024 (7)0.0059 (7)−0.0002 (7)
C10.0570 (10)0.0523 (10)0.0483 (9)−0.0023 (8)0.0075 (8)−0.0046 (8)
C20.0580 (10)0.0687 (12)0.0467 (10)0.0004 (9)0.0009 (8)−0.0034 (9)
C30.0532 (10)0.0606 (11)0.0581 (11)0.0081 (8)0.0033 (8)0.0016 (9)
C40.0490 (9)0.0505 (9)0.0538 (10)0.0010 (8)0.0081 (8)−0.0052 (8)
C50.0511 (10)0.0546 (10)0.0451 (9)−0.0018 (8)0.0045 (7)−0.0038 (8)
C60.0606 (11)0.0525 (10)0.0475 (9)0.0049 (8)0.0055 (8)−0.0008 (8)
C70.0742 (14)0.0677 (13)0.0899 (16)0.0252 (11)−0.0007 (12)−0.0115 (11)
C80.0767 (13)0.0642 (12)0.0482 (10)0.0096 (9)−0.0024 (9)0.0049 (9)
C90.0669 (11)0.0538 (10)0.0508 (10)−0.0017 (9)0.0076 (8)−0.0026 (8)
C100.0577 (10)0.0530 (10)0.0455 (9)−0.0036 (8)0.0063 (8)−0.0023 (8)
C110.0716 (12)0.0605 (11)0.0393 (9)−0.0030 (9)0.0021 (8)0.0017 (8)
C120.0707 (12)0.0508 (10)0.0472 (10)−0.0016 (8)0.0019 (8)0.0042 (8)
C130.0545 (10)0.0501 (9)0.0430 (9)−0.0058 (7)0.0053 (7)−0.0017 (7)
C140.0718 (12)0.0566 (10)0.0399 (9)−0.0004 (9)0.0073 (8)0.0030 (8)
C150.0786 (13)0.0503 (10)0.0478 (10)0.0033 (9)0.0081 (9)0.0049 (8)

Geometric parameters (Å, °)

O1—C41.366 (2)C11—C121.373 (2)
O1—C71.424 (3)C12—C131.378 (2)
O2—C51.359 (2)C13—C141.374 (2)
O2—C81.420 (2)C14—C151.376 (2)
O3—N21.225 (2)C2—H20.9300
O4—N21.214 (2)C3—H30.9300
N1—C11.423 (2)C6—H60.9300
N1—C91.260 (2)C7—H7A0.9600
N2—C131.464 (2)C7—H7B0.9600
C1—C21.379 (2)C7—H7C0.9600
C1—C61.394 (2)C8—H8A0.9600
C2—C31.390 (2)C8—H8B0.9600
C3—C41.376 (3)C8—H8C0.9600
C4—C51.403 (2)C9—H90.9300
C5—C61.375 (2)C11—H110.9300
C9—C101.467 (2)C12—H120.9300
C10—C111.394 (2)C14—H140.9300
C10—C151.388 (2)C15—H150.9300
O1···O22.5589 (18)H2···H92.2100
O1···C8i3.255 (3)H3···C72.5400
O2···C14ii3.246 (2)H3···H7B2.3400
O2···O12.5589 (18)H3···H7C2.3300
O3···C12iii3.340 (2)H6···C82.5100
O4···C8iv3.405 (3)H6···H8B2.2300
O1···H8Ci2.5500H6···H8C2.3900
O1···H14ii2.6800H7A···C4xiii3.0500
O2···H14ii2.5600H7A···C5xiii3.0900
O3···H122.4100H7A···O4ii2.8100
O3···H15v2.9200H7B···C32.7800
O3···H12iii2.8900H7B···H32.3400
O3···H9v2.6500H7C···C32.7600
O4···H142.4400H7C···H32.3300
O4···H8Civ2.5600H7C···H15xii2.5900
O4···H7Avi2.8100H8A···H11i2.5000
O4···H8Bvii2.6800H8B···C62.7000
N2···C3viii3.317 (2)H8B···H62.2300
N1···H112.6100H8B···O4xiv2.6800
C2···C13viii3.483 (2)H8C···C62.7800
C3···N2viii3.317 (2)H8C···H62.3900
C8···O4iv3.405 (3)H8C···O1ix2.5500
C8···O1ix3.255 (3)H8C···C7ix3.0900
C10···C10iv3.593 (2)H8C···O4iv2.5600
C12···O3iii3.340 (2)H9···O3x2.6500
C13···C2viii3.483 (2)H9···C22.6000
C14···O2vi3.246 (2)H9···H22.2100
C2···H92.6000H9···H152.4300
C2···H12x3.0300H11···N12.6100
C3···H7C2.7600H11···H8Aix2.5000
C3···H7B2.7800H12···O32.4100
C4···H7Axi3.0500H12···C2v3.0300
C5···H7Axi3.0900H12···O3iii2.8900
C6···H8C2.7800H14···O42.4400
C6···H8B2.7000H14···O1vi2.6800
C7···H15xii3.0900H14···O2vi2.5600
C7···H32.5400H15···O3x2.9200
C7···H8Ci3.0900H15···H92.4300
C8···H62.5100H15···C7xii3.0900
C9···H22.6800H15···H7Cxii2.5900
H2···C92.6800
C4—O1—C7117.82 (15)C1—C2—H2120.00
C5—O2—C8117.30 (13)C3—C2—H2120.00
C1—N1—C9119.65 (15)C2—C3—H3120.00
O3—N2—O4122.53 (15)C4—C3—H3120.00
O3—N2—C13118.52 (15)C1—C6—H6120.00
O4—N2—C13118.90 (14)C5—C6—H6120.00
N1—C1—C2123.93 (15)O1—C7—H7A109.00
N1—C1—C6116.99 (15)O1—C7—H7B109.00
C2—C1—C6119.02 (15)O1—C7—H7C109.00
C1—C2—C3120.56 (16)H7A—C7—H7B109.00
C2—C3—C4120.42 (15)H7A—C7—H7C109.00
O1—C4—C3125.44 (15)H7B—C7—H7C109.00
O1—C4—C5115.25 (15)O2—C8—H8A110.00
C3—C4—C5119.30 (15)O2—C8—H8B109.00
O2—C5—C4114.92 (14)O2—C8—H8C109.00
O2—C5—C6125.18 (15)H8A—C8—H8B109.00
C4—C5—C6119.88 (15)H8A—C8—H8C109.00
C1—C6—C5120.77 (15)H8B—C8—H8C109.00
N1—C9—C10122.64 (16)N1—C9—H9119.00
C9—C10—C11121.59 (16)C10—C9—H9119.00
C9—C10—C15119.79 (15)C10—C11—H11120.00
C11—C10—C15118.62 (15)C12—C11—H11120.00
C10—C11—C12120.62 (16)C11—C12—H12121.00
C11—C12—C13118.65 (15)C13—C12—H12121.00
N2—C13—C12118.37 (15)C13—C14—H14121.00
N2—C13—C14118.90 (15)C15—C14—H14121.00
C12—C13—C14122.72 (16)C10—C15—H15119.00
C13—C14—C15117.66 (16)C14—C15—H15119.00
C10—C15—C14121.69 (15)
C7—O1—C4—C5−179.92 (16)C3—C4—C5—O2−179.20 (15)
C7—O1—C4—C31.8 (2)O1—C4—C5—C6−176.25 (15)
C8—O2—C5—C6−6.9 (2)O1—C4—C5—O22.4 (2)
C8—O2—C5—C4174.56 (15)C3—C4—C5—C62.2 (2)
C1—N1—C9—C10176.12 (15)C4—C5—C6—C1−2.3 (2)
C9—N1—C1—C2−33.0 (3)O2—C5—C6—C1179.20 (15)
C9—N1—C1—C6149.95 (17)N1—C9—C10—C114.9 (3)
O3—N2—C13—C122.7 (2)N1—C9—C10—C15−175.92 (16)
O4—N2—C13—C12−174.90 (16)C9—C10—C11—C12−179.62 (15)
O3—N2—C13—C14−178.74 (16)C15—C10—C11—C121.2 (2)
O4—N2—C13—C143.6 (2)C9—C10—C15—C14178.57 (15)
N1—C1—C6—C5178.12 (15)C11—C10—C15—C14−2.2 (2)
C2—C1—C6—C50.9 (2)C10—C11—C12—C130.4 (2)
N1—C1—C2—C3−176.33 (16)C11—C12—C13—N2177.51 (15)
C6—C1—C2—C30.7 (2)C11—C12—C13—C14−1.0 (2)
C1—C2—C3—C4−0.8 (3)N2—C13—C14—C15−178.48 (15)
C2—C3—C4—O1177.65 (15)C12—C13—C14—C150.0 (2)
C2—C3—C4—C5−0.6 (2)C13—C14—C15—C101.6 (2)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, −y+2, −z+1; (iv) −x, −y+1, −z+1; (v) x, y+1, z; (vi) x, −y+1/2, z+1/2; (vii) x, −y+3/2, z+1/2; (viii) −x+1, −y+1, −z+1; (ix) −x, y+1/2, −z+1/2; (x) x, y−1, z; (xi) −x+1, y+1/2, −z+1/2; (xii) −x+1, −y, −z+1; (xiii) −x+1, y−1/2, −z+1/2; (xiv) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8C···O1ix0.962.553.255 (3)130
C8—H8C···O4iv0.962.563.405 (3)147
C14—H14···O2vi0.932.563.246 (2)131

Symmetry codes: (ix) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1; (vi) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2312).

References

  • Akkurt, M., Karaca, S., Jarrahpour, A. A., Zarei, M. & Büyükgüngör, O. (2005). Acta Cryst. E61, o776–o778.
  • Bey, P. & Vevert, J. P. (1977). Tetrahedron Lett.18, 1455–1458.
  • Bezas, B. & Zervas, L. (1961). J. Am. Chem. Soc.83, 719–722.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Fleet, G. W. J. & Fleming, I. (1969). J. Chem. Soc. C, pp. 1758–1763.
  • Lucas, R. A., Dickel, D. F., Dziemian, R. L., Ceglowski, M. J., Hensle, B. L. & MacPhillamy, H. B. (1960). J. Am. Chem. Soc.82, 5688–5693.
  • Macho, V., Kralik, M., Hudec, J. & Cingelova, J. (2004). J. Mol. Catal. A Chem.209, 69–73.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.

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