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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2828.
Published online 2010 October 20. doi:  10.1107/S1600536810040389
PMCID: PMC3009316

4-(p-Tolyl­amino)­benzaldehyde

Abstract

In the title compound, C14H13NO, the dihedral angle between the aromatic rings is 66.08 (9)°. Chains are formed along the b axis through inter­molecular N—H(...)O hydrogen bonds. The crystal structure is further stabilized by C—H(...)π inter­actions.

Related literature

For applications and bioactivity of diaryl­amines, see: Abou-Seri (2010 [triangle]); Kostrab et al. (2008 [triangle]).

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Object name is e-66-o2828-scheme1.jpg

Experimental

Crystal data

  • C14H13NO
  • M r = 211.25
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2828-efi1.jpg
  • a = 5.8356 (12) Å
  • b = 8.2581 (18) Å
  • c = 24.137 (5) Å
  • V = 1163.2 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.20 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART area-detector diffractometer
  • 6780 measured reflections
  • 1555 independent reflections
  • 1414 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.110
  • S = 1.07
  • 1555 reflections
  • 153 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810040389/zl2311sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040389/zl2311Isup2.hkl

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

Acknowledgments

This study was supported by the Chinese State Education Ministry through the Scientific Research Foundation for Returned Overseas Chinese Scholars.

supplementary crystallographic information

Comment

Due to their wide range of applications and special pharmacological activities diarylamines represent an important class of chemical compounds (Abou-Seri, 2010; Kostrab et al., 2008). We report here the synthesis and the crystal structure of one such diarylamine, the title compound 4-(p-tolylamino)benzaldehyde.

The title compound, C14H13NO, consists of benzaldehyde and tolyl groups connected through a central amino nitrogen atom (Fig. 1). The dihedral angle between the aromatic rings is 66.08 (9)°. In the crystal, one-dimensional chains are formed along the b-axis through intermolecular N—H···O hydrogen bonding interactions (Fig. 2). The chains are in turn linked through weak intermolecular C—H···π contacts involving the C8–C13 phenyl ring (centroid Cg1) into a three-dimensional network structure (Table 1).

Experimental

To a magnetically stirred solution of p-toluidine (1.0 mmol) and Cs2CO3 (3.2 mmol) in dry DMF cooled by an ice bath were added chloroacetyl chloride (1.2 mmol) and 4-hydroxybenzaldehyde (1.0 mmol). The reaction mixture was then stirred for 30 min at room temperature and placed into a microwave oven (600 W, 424 K) and irradiated for 35 min. The solvent was removed under vacuum and water (20 ml) was added to the residue. The mixture was then extracted with ethyl acetate (4 × 30 ml). The combined organic layers were dried over anhydrous MgSO4 and evaporated under vacuum to give the crude product. The product was purified by column chromatography on silica gel using ethyl acetate/petroleum ether (yield 89%). Mp 358-362 K; 1H NMR (300 MHz, CDCl3): δ 2.35 (s, 3H; CH3), 6.20 (s, 1H; NH), 6.95 (d, J = 8.4 Hz, 2H; ArH), 7.10 (d, J = 8.1 Hz, 2H; ArH), 7.18 (d, J = 8.1 Hz, 2H; ArH), 7.72 (d, J = 8.4 Hz, 2H; ArH), 9.77 (s, 1H; CHO). 13C NMR (75 MHz, CDCl3): δ 20.8 (CH3), 113.9 (CH), 122.1 (CH), 128.1 (C), 130.1 (CH), 132.1 (CH), 134.0 (C), 137.2 (C), 150.5 (C), 190.3 (CHO). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid dissolved in ethyl acetate/petroleum ether at room temperature for 5 days.

Refinement

In the absence of significant anomalous dispersion effects, Friedel pairs were merged.

Aromatic and methyl H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aryl and 0.96 Å for methyl H atoms, and with Uiso(H) =1.2Ueq(C) for aryl Hatoms, and 1.5Ueq(C) for methyl H atoms. The aldehyde (C14) and N-bound H-atoms were located in a difference Fourier map and their positions and Uiso values were freely refined.

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound. Intermolecular hydrogen bonds and C—H···π contacts are shown as dashed lines.

Crystal data

C14H13NODx = 1.206 Mg m3
Mr = 211.25Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 3865 reflections
a = 5.8356 (12) Åθ = 2.6–27.0°
b = 8.2581 (18) ŵ = 0.08 mm1
c = 24.137 (5) ÅT = 298 K
V = 1163.2 (4) Å3Block, brown
Z = 40.20 × 0.20 × 0.10 mm
F(000) = 448

Data collection

Bruker SMART area-detector diffractometer1414 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
graphiteθmax = 27.4°, θmin = 2.6°
phi and ω scansh = −7→7
6780 measured reflectionsk = −10→7
1555 independent reflectionsl = −31→24

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.07w = 1/[σ2(Fo2) + (0.0662P)2 + 0.0847P] where P = (Fo2 + 2Fc2)/3
1555 reflections(Δ/σ)max < 0.001
153 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = −0.16 e Å3

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
C131.3763 (3)0.6409 (2)0.06501 (7)0.0509 (4)
H131.46150.54910.05640.061*
C111.3240 (3)0.9306 (2)0.05882 (6)0.0506 (4)
C81.1747 (3)0.6263 (2)0.09648 (6)0.0490 (4)
C121.4480 (3)0.7908 (2)0.04698 (6)0.0502 (4)
H121.58230.79880.02640.060*
C50.9454 (3)0.4459 (2)0.15636 (7)0.0537 (4)
C101.1209 (3)0.9158 (2)0.08968 (7)0.0536 (4)
H101.03481.00770.09760.064*
N11.1016 (3)0.4765 (2)0.11257 (7)0.0638 (5)
C91.0479 (3)0.7677 (2)0.10832 (7)0.0530 (4)
H90.91370.76030.12890.064*
C30.8304 (3)0.4783 (2)0.25130 (7)0.0588 (5)
H30.85610.52390.28600.071*
C20.6412 (3)0.3791 (2)0.24364 (8)0.0568 (4)
C141.4066 (4)1.0868 (2)0.03930 (8)0.0650 (5)
C60.7577 (4)0.3455 (3)0.14822 (9)0.0667 (5)
H60.73210.29950.11360.080*
C70.6087 (4)0.3136 (3)0.19139 (9)0.0682 (5)
H70.48340.24640.18520.082*
C40.9812 (3)0.5110 (2)0.20869 (8)0.0587 (5)
H41.10760.57700.21510.070*
C10.4755 (4)0.3446 (3)0.29038 (9)0.0733 (6)
H1A0.52560.39950.32330.110*
H1B0.47020.23010.29720.110*
H1C0.32550.38230.28030.110*
O21.3205 (4)1.21695 (17)0.04864 (7)0.0910 (6)
H11.162 (5)0.393 (3)0.0987 (10)0.076 (7)*
H141.551 (5)1.074 (3)0.0161 (11)0.087 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C130.0529 (9)0.0508 (9)0.0490 (8)0.0106 (8)0.0053 (7)−0.0020 (7)
C110.0570 (9)0.0502 (9)0.0446 (7)0.0004 (8)0.0003 (7)−0.0041 (7)
C80.0523 (8)0.0529 (8)0.0419 (7)0.0040 (8)0.0004 (7)0.0004 (7)
C120.0486 (8)0.0565 (9)0.0454 (8)0.0030 (8)0.0047 (7)−0.0030 (7)
C50.0563 (9)0.0489 (8)0.0558 (9)0.0009 (9)0.0032 (8)0.0065 (7)
C100.0582 (10)0.0513 (9)0.0514 (8)0.0125 (8)0.0035 (8)−0.0045 (7)
N10.0748 (11)0.0499 (8)0.0666 (10)0.0029 (9)0.0189 (9)0.0005 (7)
C90.0491 (8)0.0585 (9)0.0513 (8)0.0074 (8)0.0073 (8)−0.0002 (7)
C30.0582 (9)0.0669 (11)0.0514 (9)−0.0040 (9)−0.0042 (8)0.0070 (8)
C20.0509 (9)0.0592 (10)0.0603 (10)0.0016 (9)−0.0016 (8)0.0133 (8)
C140.0802 (14)0.0515 (10)0.0634 (10)−0.0061 (11)0.0099 (11)−0.0073 (8)
C60.0773 (13)0.0638 (11)0.0591 (10)−0.0120 (11)−0.0060 (10)−0.0020 (9)
C70.0612 (11)0.0691 (12)0.0744 (11)−0.0182 (11)−0.0038 (10)0.0073 (10)
C40.0516 (9)0.0642 (10)0.0602 (10)−0.0113 (9)−0.0036 (8)0.0056 (8)
C10.0611 (11)0.0859 (14)0.0727 (12)−0.0038 (12)0.0070 (10)0.0197 (11)
O20.1203 (14)0.0497 (8)0.1029 (12)0.0005 (10)0.0241 (11)−0.0093 (8)

Geometric parameters (Å, °)

C13—C121.377 (3)C9—H90.9300
C13—C81.406 (3)C3—C41.380 (3)
C13—H130.9300C3—C21.387 (3)
C11—C121.392 (2)C3—H30.9300
C11—C101.405 (3)C2—C71.385 (3)
C11—C141.455 (3)C2—C11.513 (3)
C8—N11.365 (2)C14—O21.208 (3)
C8—C91.411 (2)C14—H141.02 (3)
C12—H120.9300C6—C71.383 (3)
C5—C61.388 (3)C6—H60.9300
C5—C41.388 (3)C7—H70.9300
C5—N11.419 (2)C4—H40.9300
C10—C91.371 (2)C1—H1A0.9600
C10—H100.9300C1—H1B0.9600
N1—H10.84 (2)C1—H1C0.9600
C12—C13—C8120.13 (16)C4—C3—C2121.58 (17)
C12—C13—H13119.9C4—C3—H3119.2
C8—C13—H13119.9C2—C3—H3119.2
C12—C11—C10118.36 (16)C7—C2—C3117.45 (17)
C12—C11—C14119.75 (17)C7—C2—C1121.18 (18)
C10—C11—C14121.89 (17)C3—C2—C1121.36 (18)
N1—C8—C13119.53 (16)O2—C14—C11126.2 (2)
N1—C8—C9121.91 (16)O2—C14—H14122.7 (14)
C13—C8—C9118.50 (16)C11—C14—H14111.1 (14)
C13—C12—C11121.52 (16)C7—C6—C5120.24 (19)
C13—C12—H12119.2C7—C6—H6119.9
C11—C12—H12119.2C5—C6—H6119.9
C6—C5—C4118.60 (16)C6—C7—C2121.70 (19)
C6—C5—N1120.55 (17)C6—C7—H7119.1
C4—C5—N1120.81 (17)C2—C7—H7119.1
C9—C10—C11120.89 (16)C3—C4—C5120.41 (17)
C9—C10—H10119.6C3—C4—H4119.8
C11—C10—H10119.6C5—C4—H4119.8
C8—N1—C5125.06 (16)C2—C1—H1A109.5
C8—N1—H1119.7 (17)C2—C1—H1B109.5
C5—N1—H1114.8 (17)H1A—C1—H1B109.5
C10—C9—C8120.59 (16)C2—C1—H1C109.5
C10—C9—H9119.7H1A—C1—H1C109.5
C8—C9—H9119.7H1B—C1—H1C109.5

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C13 ring.
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.84 (3)2.11 (3)2.934 (2)167 (2)
C1—H1A···Cg1ii0.962.913.613 (2)131
C12—H12···Cg1iii0.932.773.527 (2)140

Symmetry codes: (i) x, y−1, z; (ii) −x+2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2311).

References

  • Abou-Seri, S. M. (2010). Eur. J. Med. Chem.45, 4113–4121. [PubMed]
  • Bruker (2004). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kostrab, G., Lovi, M., Janotka, I., Bajus, M. & Mravec, D. (2008). Appl. Catal. A, 335, 74-81.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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