4-(p-Tolyl­amino)­benzaldehyde

Tian, X.; Xie, Y.-S.; Zuo, H.

doi:10.1107/S1600536810040389

organic compounds

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Volume 66| Part 11| November 2010| Page o2828

https://doi.org/10.1107/S1600536810040389

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4-(p-Tolylamino)benzaldehyde

Xiao Tian,^a Yong-Sheng Xie ^b and Hua Zuo ^a ^*

^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 26 September 2010; accepted 8 October 2010; online 20 October 2010)

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 ); Kostrab et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₃NO
M_r = 211.25
Orthorhombic, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.038
wR(F²) = 0.110
S = 1.07
1555 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.84 (3)	2.11 (3)	2.934 (2)	167 (2)
C1—H1A⋯Cg1ⁱⁱ	0.96	2.91	3.613 (2)	131
C12—H12⋯Cg1ⁱⁱⁱ	0.93	2.77	3.527 (2)	140
Symmetry codes: (i) x, y-1, z; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040389/zl2311Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

For applications and bioactivity of diarylamines, see: Abou-Seri (2010); Kostrab 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: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	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.

4-(p-Tolylamino)benzaldehyde top

Crystal data top

C₁₄H₁₃NO	D_x = 1.206 Mg m⁻³
M_r = 211.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 3865 reflections
a = 5.8356 (12) Å	θ = 2.6–27.0°
b = 8.2581 (18) Å	µ = 0.08 mm⁻¹
c = 24.137 (5) Å	T = 298 K
V = 1163.2 (4) Å³	Block, brown
Z = 4	0.20 × 0.20 × 0.10 mm
F(000) = 448

Data collection top

Bruker SMART area-detector diffractometer	1414 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 27.4°, θ_min = 2.6°
phi and ω scans	h = −7→7
6780 measured reflections	k = −10→7
1555 independent reflections	l = −31→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0662P)² + 0.0847P] where P = (F_o² + 2F_c²)/3
1555 reflections	(Δ/σ)_max < 0.001
153 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₄H₁₃NO	V = 1163.2 (4) Å³
M_r = 211.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.8356 (12) Å	µ = 0.08 mm⁻¹
b = 8.2581 (18) Å	T = 298 K
c = 24.137 (5) Å	0.20 × 0.20 × 0.10 mm

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.12 e Å⁻³
1555 reflections	Δρ_min = −0.16 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

	x	y	z	U_iso*/U_eq
C13	1.3763 (3)	0.6409 (2)	0.06501 (7)	0.0509 (4)
H13	1.4615	0.5491	0.0564	0.061*
C11	1.3240 (3)	0.9306 (2)	0.05882 (6)	0.0506 (4)
C8	1.1747 (3)	0.6263 (2)	0.09648 (6)	0.0490 (4)
C12	1.4480 (3)	0.7908 (2)	0.04698 (6)	0.0502 (4)
H12	1.5823	0.7988	0.0264	0.060*
C5	0.9454 (3)	0.4459 (2)	0.15636 (7)	0.0537 (4)
C10	1.1209 (3)	0.9158 (2)	0.08968 (7)	0.0536 (4)
H10	1.0348	1.0077	0.0976	0.064*
N1	1.1016 (3)	0.4765 (2)	0.11257 (7)	0.0638 (5)
C9	1.0479 (3)	0.7677 (2)	0.10832 (7)	0.0530 (4)
H9	0.9137	0.7603	0.1289	0.064*
C3	0.8304 (3)	0.4783 (2)	0.25130 (7)	0.0588 (5)
H3	0.8561	0.5239	0.2860	0.071*
C2	0.6412 (3)	0.3791 (2)	0.24364 (8)	0.0568 (4)
C14	1.4066 (4)	1.0868 (2)	0.03930 (8)	0.0650 (5)
C6	0.7577 (4)	0.3455 (3)	0.14822 (9)	0.0667 (5)
H6	0.7321	0.2995	0.1136	0.080*
C7	0.6087 (4)	0.3136 (3)	0.19139 (9)	0.0682 (5)
H7	0.4834	0.2464	0.1852	0.082*
C4	0.9812 (3)	0.5110 (2)	0.20869 (8)	0.0587 (5)
H4	1.1076	0.5770	0.2151	0.070*
C1	0.4755 (4)	0.3446 (3)	0.29038 (9)	0.0733 (6)
H1A	0.5256	0.3995	0.3233	0.110*
H1B	0.4702	0.2301	0.2972	0.110*
H1C	0.3255	0.3823	0.2803	0.110*
O2	1.3205 (4)	1.21695 (17)	0.04864 (7)	0.0910 (6)
H1	1.162 (5)	0.393 (3)	0.0987 (10)	0.076 (7)*
H14	1.551 (5)	1.074 (3)	0.0161 (11)	0.087 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C13	0.0529 (9)	0.0508 (9)	0.0490 (8)	0.0106 (8)	0.0053 (7)	−0.0020 (7)
C11	0.0570 (9)	0.0502 (9)	0.0446 (7)	0.0004 (8)	0.0003 (7)	−0.0041 (7)
C8	0.0523 (8)	0.0529 (8)	0.0419 (7)	0.0040 (8)	0.0004 (7)	0.0004 (7)
C12	0.0486 (8)	0.0565 (9)	0.0454 (8)	0.0030 (8)	0.0047 (7)	−0.0030 (7)
C5	0.0563 (9)	0.0489 (8)	0.0558 (9)	0.0009 (9)	0.0032 (8)	0.0065 (7)
C10	0.0582 (10)	0.0513 (9)	0.0514 (8)	0.0125 (8)	0.0035 (8)	−0.0045 (7)
N1	0.0748 (11)	0.0499 (8)	0.0666 (10)	0.0029 (9)	0.0189 (9)	0.0005 (7)
C9	0.0491 (8)	0.0585 (9)	0.0513 (8)	0.0074 (8)	0.0073 (8)	−0.0002 (7)
C3	0.0582 (9)	0.0669 (11)	0.0514 (9)	−0.0040 (9)	−0.0042 (8)	0.0070 (8)
C2	0.0509 (9)	0.0592 (10)	0.0603 (10)	0.0016 (9)	−0.0016 (8)	0.0133 (8)
C14	0.0802 (14)	0.0515 (10)	0.0634 (10)	−0.0061 (11)	0.0099 (11)	−0.0073 (8)
C6	0.0773 (13)	0.0638 (11)	0.0591 (10)	−0.0120 (11)	−0.0060 (10)	−0.0020 (9)
C7	0.0612 (11)	0.0691 (12)	0.0744 (11)	−0.0182 (11)	−0.0038 (10)	0.0073 (10)
C4	0.0516 (9)	0.0642 (10)	0.0602 (10)	−0.0113 (9)	−0.0036 (8)	0.0056 (8)
C1	0.0611 (11)	0.0859 (14)	0.0727 (12)	−0.0038 (12)	0.0070 (10)	0.0197 (11)
O2	0.1203 (14)	0.0497 (8)	0.1029 (12)	0.0005 (10)	0.0241 (11)	−0.0093 (8)

Geometric parameters (Å, º) top

C13—C12	1.377 (3)	C9—H9	0.9300
C13—C8	1.406 (3)	C3—C4	1.380 (3)
C13—H13	0.9300	C3—C2	1.387 (3)
C11—C12	1.392 (2)	C3—H3	0.9300
C11—C10	1.405 (3)	C2—C7	1.385 (3)
C11—C14	1.455 (3)	C2—C1	1.513 (3)
C8—N1	1.365 (2)	C14—O2	1.208 (3)
C8—C9	1.411 (2)	C14—H14	1.02 (3)
C12—H12	0.9300	C6—C7	1.383 (3)
C5—C6	1.388 (3)	C6—H6	0.9300
C5—C4	1.388 (3)	C7—H7	0.9300
C5—N1	1.419 (2)	C4—H4	0.9300
C10—C9	1.371 (2)	C1—H1A	0.9600
C10—H10	0.9300	C1—H1B	0.9600
N1—H1	0.84 (2)	C1—H1C	0.9600

C12—C13—C8	120.13 (16)	C4—C3—C2	121.58 (17)
C12—C13—H13	119.9	C4—C3—H3	119.2
C8—C13—H13	119.9	C2—C3—H3	119.2
C12—C11—C10	118.36 (16)	C7—C2—C3	117.45 (17)
C12—C11—C14	119.75 (17)	C7—C2—C1	121.18 (18)
C10—C11—C14	121.89 (17)	C3—C2—C1	121.36 (18)
N1—C8—C13	119.53 (16)	O2—C14—C11	126.2 (2)
N1—C8—C9	121.91 (16)	O2—C14—H14	122.7 (14)
C13—C8—C9	118.50 (16)	C11—C14—H14	111.1 (14)
C13—C12—C11	121.52 (16)	C7—C6—C5	120.24 (19)
C13—C12—H12	119.2	C7—C6—H6	119.9
C11—C12—H12	119.2	C5—C6—H6	119.9
C6—C5—C4	118.60 (16)	C6—C7—C2	121.70 (19)
C6—C5—N1	120.55 (17)	C6—C7—H7	119.1
C4—C5—N1	120.81 (17)	C2—C7—H7	119.1
C9—C10—C11	120.89 (16)	C3—C4—C5	120.41 (17)
C9—C10—H10	119.6	C3—C4—H4	119.8
C11—C10—H10	119.6	C5—C4—H4	119.8
C8—N1—C5	125.06 (16)	C2—C1—H1A	109.5
C8—N1—H1	119.7 (17)	C2—C1—H1B	109.5
C5—N1—H1	114.8 (17)	H1A—C1—H1B	109.5
C10—C9—C8	120.59 (16)	C2—C1—H1C	109.5
C10—C9—H9	119.7	H1A—C1—H1C	109.5
C8—C9—H9	119.7	H1B—C1—H1C	109.5

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.84 (3)	2.11 (3)	2.934 (2)	167 (2)
C1—H1A···Cg1ⁱⁱ	0.96	2.91	3.613 (2)	131
C12—H12···Cg1ⁱⁱⁱ	0.93	2.77	3.527 (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.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO
M_r	211.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	5.8356 (12), 8.2581 (18), 24.137 (5)
V (Å³)	1163.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6780, 1555, 1414
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.110, 1.07
No. of reflections	1555
No. of parameters	153
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C8–C13 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.84 (3)	2.11 (3)	2.934 (2)	167 (2)
C1—H1A···Cg1ⁱⁱ	0.96	2.91	3.613 (2)	131
C12—H12···Cg1ⁱⁱⁱ	0.93	2.77	3.527 (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.

Acknowledgements

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

References

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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2828

https://doi.org/10.1107/S1600536810040389

Open

access