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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 11| November 2010| Page o2827
https://doi.org/10.1107/S1600536810040626

4-(o-Tolyl­amino)­benzaldehyde

Li-Ying Wang,a Yong-Sheng Xie,b Ren-Min Wua and Hua Zuoa*

aCollege of Pharmaceutical Sciences, Southwest University, Chongqing 400715, People's Republic of China, and bSchool of Chemical and Environmental Engineering, Chongqing Three Gorges University, Chongqing 404100, People's Republic of China
*Correspondence e-mail: zuohua@swu.edu.cn

(Received 27 September 2010; accepted 10 October 2010; online 20 October 2010)

In the title compound, C14H13NO, the dihedral angle between the aromatic rings is 49.64 (18)°. The crystal structure is stabilized by N—H⋯O, C—H⋯O and C—H⋯π hydrogen bonds.

Related literature

For applications and bioactivity of diaryl­amines, see: Ohta et al. (2008[Ohta, K., Chiba, Y., Ogawa, T. & Endo, Y. (2008). Bioorg. Med. Chem. Lett. 18, 5050-5053.]); Li et al. (2008[Li, S. L., Ai, X. P., Feng, J. K., Cao, Y. L. & Yang, H. X. (2008). J. Power Sources, 184, 553-556.]).

[Scheme 1]

Experimental

Crystal data

  • C14H13NO

  • Mr = 211.25

  • Orthorhombic, P c a 21

  • a = 14.193 (10) Å

  • b = 10.699 (10) Å

  • c = 7.677 (6) Å

  • V = 1165.9 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 273 K

  • 0.20 × 0.15 × 0.05 mm
Data collection

  • Bruker SMART CCD area-detector diffractometer

  • 6127 measured reflections

  • 1397 independent reflections

  • 1140 reflections with I > 2σ(I)

  • Rint = 0.033
Refinement

  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.157

  • S = 1.06

  • 1397 reflections

  • 153 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C13 tolyl ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O1i 0.79 (4) 2.32 (4) 3.099 (5) 171 (3)
C14—H14A⋯O1i 0.96 2.48 3.334 (6) 148
C9—H9⋯Cg1ii 0.93 2.95 3.603 (5) 128
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+1, z]; (ii) [-x+2, -y+2, z-{\script{1\over 2}}].

Data collection: SMART (Bruker, 2004[Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810040626/si2297sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040626/si2297Isup2.hkl

checkCIF report


Comment top

Diarylamines represent an important class of compounds due to their wide applications and special pharmacological activities (Ohta et al. 2008; Li et al. (2008).). We report here the synthesis and the crystal structure of the title compound, C14H13NO, which consists of benzaldehyde and tolyl groups attached at the terminal nitrogen atoms (Fig. 1). The dihedral angle between the aromatic rings is 49.64 (18)°. The N1, C14 and H14A atoms are coplanar with the phenyl ring C8 to C13, with deviations of -0.053 (3) Å, -0.076 (4) Å, and -0.07 (1) Å from the ring plane, respectively. The non-planar conformation of the title molecule is not only due to the intramolecular C14-H14A···N1 hydrogen bond, but also owing to the repulsion of H14A and H1 together with packing effects and intermolecular interactions (Fig. 1 and Table 1).In the crystal, zigzag chains are formed along a through the intermolecular N—H···O and C—H···O hydrogen bonds (Fig. 2 and Table 1). The molecules are also stabilized by weak C—H···π interactions (Table 1: Cg1ii is the centroid of the tolyl ring C8 - C13).

Related literature top

For applications and bioactivity of diarylamines, see: Ohta et al. (2008); Li et al. (2008).

Experimental top

To a magnetically stirred solution of o-toluidine (1.0 mmol) and Cs2CO3 (3.2 mmol) in dry DMF cooled by 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, 423K) and irradiated for 35 min. The solvent was removed under vacuum and water (20 ml) was added into the residue. The mixture was then extracted by ethyl acetate (4 x 30 ml). The combined organic layers were dried over anhydrous MgSO4 and evaporated under vacuum to give the crude product, which was purified by column chromatography on silica gel using ethyl acetate/petroleum ether (yield 89%). 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 4 days.

Refinement top

All 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 H atoms, and 1.5Ueq(C) for methyl H atoms. The C1- and N1-bound H-atoms were located in a difference Fourier map, the Uiso values were freely refined. In the absence of significant anomalous dispersion effects, Friedel pairs were averaged.

Structure description top

Diarylamines represent an important class of compounds due to their wide applications and special pharmacological activities (Ohta et al. 2008; Li et al. (2008).). We report here the synthesis and the crystal structure of the title compound, C14H13NO, which consists of benzaldehyde and tolyl groups attached at the terminal nitrogen atoms (Fig. 1). The dihedral angle between the aromatic rings is 49.64 (18)°. The N1, C14 and H14A atoms are coplanar with the phenyl ring C8 to C13, with deviations of -0.053 (3) Å, -0.076 (4) Å, and -0.07 (1) Å from the ring plane, respectively. The non-planar conformation of the title molecule is not only due to the intramolecular C14-H14A···N1 hydrogen bond, but also owing to the repulsion of H14A and H1 together with packing effects and intermolecular interactions (Fig. 1 and Table 1).In the crystal, zigzag chains are formed along a through the intermolecular N—H···O and C—H···O hydrogen bonds (Fig. 2 and Table 1). The molecules are also stabilized by weak C—H···π interactions (Table 1: Cg1ii is the centroid of the tolyl ring C8 - C13).

For applications and bioactivity of diarylamines, see: Ohta et al. (2008); Li et al. (2008).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. A section of the crystal packing of the title compound. Intermolecular hydrogen bonds are shown by dashed lines.
4-(o-Tolylamino)benzaldehyde top
Crystal data top
C14H13NODx = 1.204 Mg m−3
Mr = 211.25Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21Cell parameters from 2572 reflections
a = 14.193 (10) Åθ = 2.4–26.6°
b = 10.699 (10) ŵ = 0.08 mm−1
c = 7.677 (6) ÅT = 273 K
V = 1165.9 (16) Å3Plate, brown
Z = 40.20 × 0.15 × 0.05 mm
F(000) = 448
Data collection top
Bruker SMART CCD area-detector
diffractometer		1140 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.033
Graphite monochromatorθmax = 27.4°, θmin = 1.9°
phi and ω scansh = −18→14
6127 measured reflectionsk = −13→13
1397 independent reflectionsl = −6→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.1027P)2 + 0.0736P]
where P = (Fo2 + 2Fc2)/3
1397 reflections(Δ/σ)max < 0.001
153 parametersΔρmax = 0.22 e Å−3
1 restraintΔρmin = −0.21 e Å−3
Crystal data top
C14H13NOV = 1165.9 (16) Å3
Mr = 211.25Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 14.193 (10) ŵ = 0.08 mm−1
b = 10.699 (10) ÅT = 273 K
c = 7.677 (6) Å0.20 × 0.15 × 0.05 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1140 reflections with I > 2σ(I)
6127 measured reflectionsRint = 0.033
1397 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0501 restraint
wR(F2) = 0.157H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.22 e Å−3
1397 reflectionsΔρmin = −0.21 e Å−3
153 parameters
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 > 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) top
xyzUiso*/Ueq
C61.07328 (19)0.7362 (2)0.3779 (5)0.0546 (7)
H61.07750.80920.44320.066*
C50.99125 (16)0.7114 (2)0.2798 (4)0.0476 (6)
N10.91447 (16)0.7907 (2)0.2760 (4)0.0567 (7)
C80.91320 (18)0.9212 (2)0.3158 (4)0.0496 (7)
C40.98692 (19)0.5966 (2)0.1871 (5)0.0534 (7)
H40.93240.57580.12650.064*
C31.0628 (2)0.5154 (2)0.1858 (5)0.0548 (7)
H31.05910.44180.12170.066*
C21.14506 (19)0.5424 (2)0.2797 (5)0.0531 (7)
C130.83034 (19)0.9730 (2)0.3886 (5)0.0557 (7)
O11.23816 (19)0.36802 (18)0.1876 (6)0.0897 (10)
C11.2296 (2)0.4612 (3)0.2747 (6)0.0660 (9)
C71.1475 (2)0.6520 (2)0.3770 (5)0.0581 (8)
H71.20060.66940.44370.070*
C90.9897 (2)0.9981 (3)0.2718 (5)0.0577 (7)
H91.04310.96380.22040.069*
C140.7450 (3)0.8922 (3)0.4262 (8)0.0821 (11)
H14A0.75890.80690.39680.123*
H14B0.69260.92080.35800.123*
H14C0.72950.89760.54770.123*
C120.8298 (3)1.1013 (3)0.4195 (6)0.0742 (10)
H120.77651.13710.46930.089*
C100.9854 (2)1.1256 (3)0.3053 (7)0.0728 (11)
H101.03651.17640.27810.087*
C110.9052 (3)1.1773 (3)0.3790 (7)0.0814 (12)
H110.90231.26270.40110.098*
H1A1.286 (2)0.483 (3)0.339 (5)0.063 (9)*
H10.869 (3)0.755 (3)0.244 (5)0.070 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C60.0502 (14)0.0407 (13)0.0730 (19)0.0008 (10)−0.0053 (14)−0.0097 (14)
C50.0395 (11)0.0388 (12)0.0645 (17)−0.0005 (9)0.0042 (12)−0.0001 (14)
N10.0375 (10)0.0445 (11)0.0881 (19)−0.0002 (9)−0.0052 (12)−0.0093 (14)
C80.0417 (12)0.0427 (13)0.0645 (18)0.0050 (10)−0.0062 (12)−0.0031 (13)
C40.0441 (12)0.0446 (12)0.0716 (19)−0.0062 (10)−0.0046 (14)−0.0073 (15)
C30.0586 (15)0.0355 (11)0.0704 (18)−0.0036 (11)0.0043 (15)−0.0069 (15)
C20.0487 (13)0.0375 (11)0.0730 (19)0.0034 (10)0.0040 (14)0.0039 (14)
C130.0469 (14)0.0554 (15)0.0646 (18)0.0144 (11)−0.0045 (14)0.0001 (15)
O10.0794 (16)0.0617 (12)0.128 (3)0.0276 (12)−0.0038 (18)−0.0164 (18)
C10.0559 (17)0.0496 (15)0.093 (3)0.0101 (13)−0.0029 (18)0.0025 (19)
C70.0478 (14)0.0446 (13)0.082 (2)0.0010 (11)−0.0105 (15)−0.0024 (15)
C90.0470 (13)0.0486 (13)0.077 (2)0.0005 (10)−0.0054 (15)0.0012 (16)
C140.0541 (16)0.090 (2)0.102 (3)0.0158 (18)0.0239 (18)0.008 (2)
C120.0644 (19)0.0643 (18)0.094 (3)0.0275 (15)−0.0133 (19)−0.015 (2)
C100.0631 (17)0.0484 (15)0.107 (3)−0.0040 (13)−0.022 (2)0.006 (2)
C110.083 (2)0.0442 (15)0.117 (3)0.0170 (17)−0.035 (2)−0.010 (2)
Geometric parameters (Å, º) top
C6—C71.386 (4)C13—C121.393 (4)
C6—C51.412 (4)C13—C141.516 (5)
C6—H60.9300O1—C11.207 (5)
C5—N11.381 (3)C1—H1A0.97 (4)
C5—C41.421 (4)C7—H70.9300
N1—C81.429 (4)C9—C101.390 (5)
N1—H10.80 (4)C9—H90.9300
C8—C91.403 (4)C14—H14A0.9600
C8—C131.415 (4)C14—H14B0.9600
C4—C31.383 (4)C14—H14C0.9600
C4—H40.9300C12—C111.381 (6)
C3—C21.403 (4)C12—H120.9300
C3—H30.9300C10—C111.386 (6)
C2—C71.391 (4)C10—H100.9300
C2—C11.481 (4)C11—H110.9300
C7—C6—C5120.1 (2)O1—C1—C2125.5 (4)
C7—C6—H6119.9O1—C1—H1A113.4 (19)
C5—C6—H6119.9C2—C1—H1A121.0 (19)
N1—C5—C6123.1 (2)C6—C7—C2122.2 (3)
N1—C5—C4119.1 (2)C6—C7—H7118.9
C6—C5—C4117.7 (2)C2—C7—H7118.9
C5—N1—C8127.2 (2)C10—C9—C8119.8 (3)
C5—N1—H1111 (2)C10—C9—H9120.1
C8—N1—H1122 (2)C8—C9—H9120.1
C9—C8—C13120.6 (2)C13—C14—H14A109.5
C9—C8—N1120.7 (2)C13—C14—H14B109.5
C13—C8—N1118.5 (2)H14A—C14—H14B109.5
C3—C4—C5120.8 (3)C13—C14—H14C109.5
C3—C4—H4119.6H14A—C14—H14C109.5
C5—C4—H4119.6H14B—C14—H14C109.5
C4—C3—C2121.0 (3)C11—C12—C13122.5 (3)
C4—C3—H3119.5C11—C12—H12118.7
C2—C3—H3119.5C13—C12—H12118.7
C7—C2—C3118.0 (2)C11—C10—C9120.2 (3)
C7—C2—C1119.3 (3)C11—C10—H10119.9
C3—C2—C1122.7 (3)C9—C10—H10119.9
C12—C13—C8117.3 (3)C12—C11—C10119.6 (3)
C12—C13—C14121.7 (3)C12—C11—H11120.2
C8—C13—C14121.1 (2)C10—C11—H11120.2
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C8–C13 tolyl ring.
D—H···AD—HH···AD···AD—H···A
C14—H14A···N10.962.402.880 (6)110
N1—H1···O1i0.79 (4)2.32 (4)3.099 (5)171 (3)
C14—H14A···O1i0.962.483.334 (6)148
C9—H9···Cg1ii0.932.953.603 (5)128
Symmetry codes: (i) x−1/2, −y+1, z; (ii) −x+2, −y+2, z−1/2.

Experimental details

Crystal data
Chemical formulaC14H13NO
Mr211.25
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)273
a, b, c (Å)14.193 (10), 10.699 (10), 7.677 (6)
V (Å3)1165.9 (16)
Z4
Radiation typeMo Kα
µ (mm−1)0.08
Crystal size (mm)0.20 × 0.15 × 0.05
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		6127, 1397, 1140
Rint0.033
(sin θ/λ)max (Å−1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.157, 1.06
No. of reflections1397
No. of parameters153
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.22, −0.21

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C8–C13 tolyl ring.
D—H···AD—HH···AD···AD—H···A
C14—H14A···N10.962.402.880 (6)110
N1—H1···O1i0.79 (4)2.32 (4)3.099 (5)171 (3)
C14—H14A···O1i0.962.483.334 (6)148
C9—H9···Cg1ii0.932.953.603 (5)128
Symmetry codes: (i) x−1/2, −y+1, z; (ii) −x+2, −y+2, z−1/2.
 

Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities, P. R. China (XDJK2009C080).

References

First citationBruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationLi, S. L., Ai, X. P., Feng, J. K., Cao, Y. L. & Yang, H. X. (2008). J. Power Sources, 184, 553–556.  Web of Science CrossRef CAS Google Scholar
 First citationOhta, K., Chiba, Y., Ogawa, T. & Endo, Y. (2008). Bioorg. Med. Chem. Lett. 18, 5050–5053.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 11| November 2010| Page o2827
https://doi.org/10.1107/S1600536810040626
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