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Acta Cryst. (2008). E64, o2291    [ doi:10.1107/S1600536808036015 ]

3-Methoxy-4-(4-nitrobenzyloxy)benzaldehyde

M. Li and X. Chen

Abstract top

In the title compound, C15H13NO5, the vanillin group makes a dihedral angle of 4.95 (8)° with the benzene ring of the nitrobenzene group. The packing is stabilized by weak, non-classical intermolecular C-H...O interactions which link molecules into chains running along the c axis.

Comment top

Schiff-base ligands have received a good deal of attention in biology and chemistry (Kahwa et al., 1986). Many Schiff base derivatives have been synthesized and employed to develop protein and enzyme mimics (Santos et al., 2001). As a part of our interest in the coordination properties of Schiff bases functioning as ligands, we investigated the title compound, (I), used as a precursor in the preparation of Schiff bases.

In the title molecule (Fig. 1), bond lengths and angles are within normal ranges (Allen et al., 1987). The vanillin group (C1—C7/O3/O4) is essentially planar (except the methyl H atoms), with an r.m.s. deviation for fitted atoms of 0.035 (3) Å. This group makes a dihedral angle of 4.95 (8)° with the benzene ring (C10—C15) of the nitrobenzene group.

The crystal packing is stabilized by weak, non-classical intermolecular C14—H14···O5═C7 interactions that link adjacent molecules into one-dimensional chains running along the c axis (Table 1, Fig. 2).

Related literature top

For general background on Schiff bases, see: Kahwa et al. (1986); Santos et al. (2001). For bond-length data, see: Allen et al. (1987);

Experimental top

An anhydrous acetonitrile solution (100 ml) of 4-hydroxy-3-methoxybenzaldehyde (1.52 g, 10 mmol) was added dropwise to a solution (50 ml) of 1-(bromomethyl)-4-nitrobenzene (2.16 g, 10 mmol) and pyridine (0.79 g, 10 mmol) in acetonitrile, in 30 min., and the mixture refluxed for 24 h under nitrogen atmosphere. The solvent was removed and the resultant mixture poured into ice-water (100 ml). The yellow precipitate was then isolated and recrystallized from acetonitrile, and then dried in a vacuum to give the pure compound in 74% yield. Pale-yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.

Refinement top

The H atoms were included in calculated positions and refined using a riding model approximation. Constrained C—H bond lengths and isotropic U parameters: 0.93 Å and Uiso(H) = 1.2Ueq(C) for Csp2—H; 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene C—H; 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl C—H.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids for non-H atoms drawn at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram for (I), with H bonds drawn as dashed lines.
3-Methoxy-4-(4-nitrobenzyloxy)benzaldehyde top
Crystal data top
C15H13NO5F(000) = 1200
Mr = 287.26Dx = 1.353 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3156 reflections
a = 13.743 (3) Åθ = 2.2–26.5°
b = 12.526 (3) ŵ = 0.10 mm−1
c = 16.384 (3) ÅT = 294 K
V = 2820.4 (10) Å3Block, pale-yellow
Z = 80.23 × 0.18 × 0.12 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2877 independent reflections
Radiation source: fine-focus sealed tube1540 reflections with I > 2σ(I)
graphiteRint = 0.045
φ and ω scansθmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→17
Tmin = 0.932, Tmax = 0.988k = −14→15
15172 measured reflectionsl = −20→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.132 w = 1/[σ2(Fo2) + (0.0424P)2 + 1.1393P]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
2877 reflectionsΔρmax = 0.16 e Å−3
192 parametersΔρmin = −0.17 e Å−3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0017 (5)
Crystal data top
C15H13NO5V = 2820.4 (10) Å3
Mr = 287.26Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 13.743 (3) ŵ = 0.10 mm−1
b = 12.526 (3) ÅT = 294 K
c = 16.384 (3) Å0.23 × 0.18 × 0.12 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2877 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1540 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.988Rint = 0.045
15172 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.16 e Å−3
S = 0.99Δρmin = −0.17 e Å−3
2877 reflectionsAbsolute structure: ?
192 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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 > 2σ(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) top
xyzUiso*/Ueq
N10.14273 (18)−0.3678 (2)1.20564 (17)0.0880 (7)
O10.1166 (2)−0.34357 (19)1.27401 (14)0.1320 (9)
O20.1674 (2)−0.45767 (19)1.18670 (15)0.1303 (9)
O30.11868 (11)0.05467 (12)0.99132 (8)0.0671 (5)
O40.07376 (11)0.23118 (12)1.05892 (9)0.0705 (5)
O50.1082 (2)0.5139 (2)0.82786 (17)0.1500 (12)
C10.09685 (14)0.23830 (18)0.97787 (13)0.0570 (5)
C20.09799 (15)0.33013 (19)0.93261 (15)0.0671 (6)
H20.08260.39500.95700.081*
C30.12223 (16)0.3267 (2)0.84953 (16)0.0739 (7)
C40.14582 (18)0.2313 (2)0.81422 (15)0.0772 (7)
H40.16260.22940.75920.093*
C50.14517 (17)0.1375 (2)0.85877 (14)0.0704 (7)
H50.16100.07300.83400.085*
C60.12076 (15)0.14069 (17)0.94062 (13)0.0572 (6)
C70.1230 (2)0.4259 (3)0.8018 (2)0.1087 (12)
H70.13610.41990.74630.130*
C80.0516 (2)0.3282 (2)1.10024 (16)0.0976 (10)
H8A0.10710.37471.09850.146*
H8B0.03540.31301.15600.146*
H8C−0.00270.36231.07410.146*
C90.14047 (18)−0.04690 (17)0.95782 (13)0.0680 (6)
H9A0.2033−0.04470.93090.082*
H9B0.0917−0.06600.91760.082*
C100.14211 (15)−0.12841 (17)1.02476 (13)0.0562 (5)
C110.16208 (16)−0.23375 (19)1.00431 (14)0.0665 (6)
H110.1746−0.25160.95020.080*
C120.16355 (17)−0.31198 (19)1.06322 (16)0.0707 (7)
H120.1777−0.38241.04960.085*
C130.14380 (16)−0.28411 (19)1.14254 (15)0.0637 (6)
C140.12433 (18)−0.18140 (19)1.16476 (14)0.0709 (7)
H140.1117−0.16441.21900.085*
C150.12358 (17)−0.10322 (19)1.10550 (14)0.0668 (6)
H150.1105−0.03291.12000.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0997 (17)0.0762 (17)0.0882 (18)−0.0093 (13)−0.0130 (14)0.0156 (14)
O10.212 (3)0.1117 (17)0.0727 (14)−0.0042 (16)0.0010 (16)0.0221 (13)
O20.177 (2)0.0729 (15)0.141 (2)0.0080 (15)0.0028 (17)0.0271 (14)
O30.0910 (12)0.0563 (10)0.0541 (9)0.0010 (8)0.0058 (8)−0.0018 (7)
O40.0939 (12)0.0657 (10)0.0520 (9)0.0107 (8)0.0013 (8)−0.0026 (8)
O50.175 (3)0.1065 (19)0.169 (2)0.0499 (18)0.0663 (19)0.0703 (18)
C10.0525 (12)0.0661 (15)0.0524 (12)−0.0001 (10)−0.0015 (10)0.0039 (11)
C20.0595 (14)0.0662 (15)0.0757 (16)0.0055 (11)0.0020 (12)0.0117 (12)
C30.0561 (14)0.0888 (19)0.0768 (17)0.0040 (13)0.0062 (12)0.0297 (15)
C40.0726 (16)0.104 (2)0.0555 (14)−0.0001 (15)0.0069 (12)0.0140 (15)
C50.0762 (16)0.0778 (17)0.0573 (14)−0.0025 (13)0.0029 (12)−0.0004 (13)
C60.0584 (13)0.0597 (14)0.0536 (13)−0.0043 (10)−0.0026 (10)0.0043 (11)
C70.090 (2)0.122 (3)0.114 (2)0.029 (2)0.0266 (18)0.057 (2)
C80.148 (3)0.0751 (19)0.0700 (16)0.0201 (18)−0.0029 (17)−0.0147 (14)
C90.0865 (17)0.0611 (15)0.0563 (13)0.0032 (12)0.0080 (12)−0.0068 (11)
C100.0538 (12)0.0587 (14)0.0562 (13)−0.0018 (10)0.0038 (10)−0.0046 (10)
C110.0712 (15)0.0645 (16)0.0640 (14)0.0029 (12)0.0158 (11)−0.0088 (12)
C120.0698 (15)0.0577 (15)0.0847 (18)0.0049 (11)0.0114 (13)−0.0043 (13)
C130.0598 (13)0.0628 (15)0.0685 (15)−0.0028 (11)−0.0047 (12)0.0070 (12)
C140.0905 (18)0.0715 (17)0.0509 (13)−0.0038 (13)−0.0053 (12)−0.0051 (12)
C150.0865 (17)0.0584 (14)0.0555 (14)−0.0008 (12)−0.0029 (12)−0.0085 (11)
Geometric parameters (Å, °) top
N1—O11.215 (3)C7—H70.9300
N1—O21.216 (3)C8—H8A0.9600
N1—C131.472 (3)C8—H8B0.9600
O3—C61.361 (2)C8—H8C0.9600
O3—C91.418 (2)C9—C101.499 (3)
O4—C11.368 (2)C9—H9A0.9700
O4—C81.424 (3)C9—H9B0.9700
O5—C71.199 (4)C10—C151.384 (3)
C1—C21.369 (3)C10—C111.389 (3)
C1—C61.406 (3)C11—C121.376 (3)
C2—C31.402 (3)C11—H110.9300
C2—H20.9300C12—C131.373 (3)
C3—C41.367 (3)C12—H120.9300
C3—C71.468 (4)C13—C141.364 (3)
C4—C51.383 (3)C14—C151.379 (3)
C4—H40.9300C14—H140.9300
C5—C61.383 (3)C15—H150.9300
C5—H50.9300
O1—N1—O2123.3 (3)H8A—C8—H8B109.5
O1—N1—C13118.2 (3)O4—C8—H8C109.5
O2—N1—C13118.5 (3)H8A—C8—H8C109.5
C6—O3—C9118.02 (16)H8B—C8—H8C109.5
C1—O4—C8117.09 (18)O3—C9—C10109.34 (17)
O4—C1—C2125.7 (2)O3—C9—H9A109.8
O4—C1—C6114.77 (19)C10—C9—H9A109.8
C2—C1—C6119.5 (2)O3—C9—H9B109.8
C1—C2—C3120.2 (2)C10—C9—H9B109.8
C1—C2—H2119.9H9A—C9—H9B108.3
C3—C2—H2119.9C15—C10—C11118.9 (2)
C4—C3—C2119.6 (2)C15—C10—C9122.8 (2)
C4—C3—C7120.9 (3)C11—C10—C9118.28 (19)
C2—C3—C7119.5 (3)C12—C11—C10120.7 (2)
C3—C4—C5121.2 (2)C12—C11—H11119.6
C3—C4—H4119.4C10—C11—H11119.6
C5—C4—H4119.4C13—C12—C11118.7 (2)
C4—C5—C6119.3 (2)C13—C12—H12120.7
C4—C5—H5120.4C11—C12—H12120.7
C6—C5—H5120.4C14—C13—C12122.1 (2)
O3—C6—C5125.1 (2)C14—C13—N1118.8 (2)
O3—C6—C1114.76 (19)C12—C13—N1119.1 (2)
C5—C6—C1120.2 (2)C13—C14—C15118.9 (2)
O5—C7—C3126.0 (3)C13—C14—H14120.5
O5—C7—H7117.0C15—C14—H14120.5
C3—C7—H7117.0C14—C15—C10120.7 (2)
O4—C8—H8A109.5C14—C15—H15119.7
O4—C8—H8B109.5C10—C15—H15119.7
C8—O4—C1—C2−1.8 (3)C2—C3—C7—O53.3 (5)
C8—O4—C1—C6178.3 (2)C6—O3—C9—C10175.41 (18)
O4—C1—C2—C3−179.5 (2)O3—C9—C10—C150.6 (3)
C6—C1—C2—C30.4 (3)O3—C9—C10—C11179.86 (19)
C1—C2—C3—C4−0.8 (3)C15—C10—C11—C12−0.1 (3)
C1—C2—C3—C7179.9 (2)C9—C10—C11—C12−179.4 (2)
C2—C3—C4—C50.7 (4)C10—C11—C12—C130.7 (3)
C7—C3—C4—C5−179.9 (2)C11—C12—C13—C14−1.0 (4)
C3—C4—C5—C6−0.4 (4)C11—C12—C13—N1178.4 (2)
C9—O3—C6—C5−1.8 (3)O1—N1—C13—C146.0 (4)
C9—O3—C6—C1179.01 (19)O2—N1—C13—C14−174.4 (2)
C4—C5—C6—O3−179.1 (2)O1—N1—C13—C12−173.5 (3)
C4—C5—C6—C10.0 (3)O2—N1—C13—C126.1 (4)
O4—C1—C6—O3−1.0 (3)C12—C13—C14—C150.6 (4)
C2—C1—C6—O3179.12 (19)N1—C13—C14—C15−178.8 (2)
O4—C1—C6—C5179.83 (19)C13—C14—C15—C100.1 (4)
C2—C1—C6—C5−0.1 (3)C11—C10—C15—C14−0.4 (3)
C4—C3—C7—O5−176.1 (3)C9—C10—C15—C14178.9 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O5i0.932.603.405 (3)146
Symmetry codes: (i) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O5i0.932.603.405 (3)146
Symmetry codes: (i) x, −y+1/2, z+1/2.
references
References top

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Kahwa, I. A., Selbin, J., Hsieh, T. C.-Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185.

Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.