4,4′-(Phenyl­imino)dibenzaldehyde

Wang, Y.-G.; Tan, X.-J.; Xing, D.-X.

doi:10.1107/S1600536809031924

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2192

doi:10.1107/S1600536809031924

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4,4′-(Phenylimino)dibenzaldehyde

Yong-Gang Wang,^a Xue-Jie Tan ^a ^* and Dian-Xiang Xing ^a

^aDepartment of Chemical Industry, Shandong Institute of Light Industry, Jinan 250353, People's Republic of China
^*Correspondence e-mail: tanxuejie@163.com

(Received 15 July 2009; accepted 12 August 2009; online 19 August 2009)

The asymmetric unit of the title compound, C₂₀H₁₅NO₂, contains one half-molecule with the central N atom and two C atoms of the benzene moiety lying on a twofold rotation axis. Weak C—H⋯O interactions join the molecules together into an infinite three-dimensional network.

Related literature

The title compound was obtained unintentionally as the product of an attempted purification of tris(4-formylphenyl)amine, which is used as a building block in materials chemistry (Thomas et al., 2005 ). For hydrogen bonding, see: Krishnamohan Sharma & Desiraju (1994 ). =

Experimental

Crystal data

C₂₀H₁₅NO₂
M_r = 301.33
Orthorhombic, P b c n
a = 8.836 (2) Å
b = 9.710 (2) Å
c = 18.621 (4) Å
V = 1597.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.32 × 0.18 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.980, T_max = 0.992
7399 measured reflections
1412 independent reflections
1087 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.187
S = 1.07
1412 reflections
136 parameters
All H-atom parameters refinemed
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H3⋯O1ⁱ	0.96 (3)	2.48 (3)	3.396 (4)	159 (3)
C9—H7⋯O1ⁱⁱ	0.95 (3)	2.55 (4)	3.495 (4)	173 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031924/jh2093sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031924/jh2093Isup2.hkl

checkCIF report

Comment top

The popularity of tris(4-formylphenyl)amine as a building block is rapidly growing in materials chemistry (Thomas et al., 2005). The title compound, (I) (Fig. 1), [C₂₀H₁₅NO₂], was obtained unintentionally as the product of an attempted purification of tris(4-formylphenyl)amine.

The molecule of (I) has three phenyl rings, but the asymmetric unit contains only one half of (I). The ring (C7 to C10) makes a dihedral angle of 70.36 (8)° with ring (C1 to C6), and a dihedral angle of 70.22 (8)° with ring (C1ⁱ to C6ⁱ) (symmetry code: (i) -x, +y, 0.5 - z). The dihedral angle of the latter two is 66.66 (8)°.

The PLATON program (Spek, 2009) suggests that there are no classic hydrogen bonds, but there are weak C—H···O hydrogen bonds (Table 2, Krishnamohan Sharma & Desiraju, 1994) between carbonyl oxygen and H atoms on the adjacent molecules, which link them into infinite three-dimensional network[Fig. 2].

Related literature top

The title compound was obtained unintentionally as the product of an attempted purification of tris(4-formylphenyl)amine, which is used as a building block in materials chemistry (Thomas et al., 2005). For hydrogen bonding, see: Krishnamohan Sharma & Desiraju (1994).

Experimental top

Phosphorus oxychloride (POCl₃) and N,N-dimethylformamide (DMF) were analytical reagent and used after the process of removing oxygen and water. Other organic solvents and common materials used for synthesis were used without further purification. The compound (I) was prepared by mixing 5.0 g triphenylamine and an ice-cooled mixture of POCl₃(47.5 mL) and DMF(36.3 mL) under N₂. The resulting mixture was stirred at 95°C for 4 h under N₂. After cooling to room temperature,the mixture was poured into ice-water(1L),and basified with 1M NaOH. After filtration, the crude product was purified by column chromatography with petroleum ether/ethyl acetate (8/1,in volume ratio) to yield I(yellow transparent crystal). Elemental analysis Calcd: C 79.72, H 5.02, N 4.65%. Found: C 79.81, H 5.16, N 4.57%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. C1I to C6I,C8I,C9I,C11I,O1I and H1I to H7I were created by GROW and the symmetry code of "I" is -x, +y, 0.5 - z.
	Fig. 2. The packing of (I), viewed down the b axis.

4,4'-(Phenylimino)dibenzaldehyde top

Crystal data top

C₂₀H₁₅NO₂	D_x = 1.253 Mg m⁻³
M_r = 301.33	Melting point = 417–419 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 378 reflections
a = 8.836 (2) Å	θ = 1.7–25.0°
b = 9.710 (2) Å	µ = 0.08 mm⁻¹
c = 18.621 (4) Å	T = 298 K
V = 1597.6 (6) Å³	Block, yellow
Z = 4	0.32 × 0.18 × 0.08 mm
F(000) = 632

Data collection top

Bruker SMART CCD area-detector diffractometer	1412 independent reflections
Radiation source: fine-focus sealed tube	1087 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
π and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.980, T_max = 0.992	k = −11→8
7399 measured reflections	l = −22→21

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)] = 0.064	Hydrogen site location: difference Fourier map
wR(F²) = 0.187	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0996P)² + 0.4228P] where P = (F_o² + 2F_c²)/3
1412 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₂₀H₁₅NO₂	V = 1597.6 (6) Å³
M_r = 301.33	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 8.836 (2) Å	µ = 0.08 mm⁻¹
b = 9.710 (2) Å	T = 298 K
c = 18.621 (4) Å	0.32 × 0.18 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1412 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1087 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.992	R_int = 0.043
7399 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.187	All H-atom parameters refined
S = 1.07	Δρ_max = 0.29 e Å⁻³
1412 reflections	Δρ_min = −0.30 e Å⁻³
136 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
C1	0.0438 (3)	0.5517 (3)	0.31252 (11)	0.0446 (6)
C2	0.1601 (3)	0.6013 (3)	0.35553 (15)	0.0587 (8)
C3	0.1977 (4)	0.5311 (3)	0.41719 (16)	0.0670 (9)
C4	0.1216 (3)	0.4133 (3)	0.43801 (13)	0.0593 (8)
C5	0.0081 (3)	0.3648 (3)	0.39479 (14)	0.0573 (7)
C6	−0.0305 (3)	0.4314 (3)	0.33246 (13)	0.0499 (7)
C7	0.0000	0.7700 (3)	0.2500	0.0458 (8)
C8	0.0651 (3)	0.8417 (3)	0.19405 (15)	0.0581 (8)
C9	0.0634 (4)	0.9841 (3)	0.19400 (18)	0.0697 (9)
C10	0.0000	1.0547 (5)	0.2500	0.0712 (12)
C11	0.1559 (5)	0.3415 (4)	0.50518 (16)	0.0873 (12)
N1	0.0000	0.6232 (3)	0.2500	0.0528 (8)
O1	0.2531 (4)	0.3709 (3)	0.54591 (13)	0.1245 (12)
H1	0.212 (3)	0.682 (3)	0.3407 (14)	0.067 (8)*
H2	0.271 (4)	0.566 (4)	0.4436 (17)	0.089 (10)*
H3	−0.041 (3)	0.282 (4)	0.4107 (16)	0.090 (10)*
H4	−0.111 (3)	0.399 (3)	0.3032 (13)	0.059 (8)*
H5	0.101 (4)	0.248 (5)	0.5133 (19)	0.113 (13)*
H6	0.106 (3)	0.790 (3)	0.1563 (16)	0.071 (8)*
H7	0.110 (3)	1.031 (3)	0.1554 (18)	0.088 (10)*
H8	0.0000	1.153 (6)	0.2500	0.092 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0513 (14)	0.0464 (14)	0.0362 (12)	0.0041 (11)	−0.0018 (10)	−0.0007 (10)
C2	0.0626 (17)	0.0572 (17)	0.0563 (16)	−0.0078 (14)	−0.0105 (13)	−0.0025 (14)
C3	0.0714 (19)	0.073 (2)	0.0566 (17)	0.0136 (16)	−0.0257 (15)	−0.0160 (16)
C4	0.086 (2)	0.0492 (15)	0.0429 (14)	0.0234 (14)	−0.0042 (14)	−0.0046 (12)
C5	0.0769 (19)	0.0508 (16)	0.0441 (14)	0.0065 (14)	0.0073 (14)	0.0005 (12)
C6	0.0540 (15)	0.0510 (15)	0.0447 (13)	−0.0005 (12)	−0.0015 (12)	−0.0007 (12)
C7	0.0535 (19)	0.0444 (19)	0.0396 (17)	0.000	−0.0017 (15)	0.000
C8	0.0658 (17)	0.0573 (18)	0.0513 (15)	0.0000 (13)	0.0066 (13)	0.0003 (13)
C9	0.081 (2)	0.0585 (19)	0.0696 (19)	−0.0096 (15)	0.0021 (16)	0.0158 (16)
C10	0.080 (3)	0.044 (2)	0.090 (3)	0.000	−0.005 (2)	0.000
C11	0.138 (3)	0.077 (2)	0.0460 (17)	0.045 (2)	−0.017 (2)	−0.0119 (17)
N1	0.072 (2)	0.0447 (17)	0.0419 (15)	0.000	−0.0079 (14)	0.000
O1	0.181 (3)	0.117 (2)	0.0762 (16)	0.059 (2)	−0.0570 (19)	−0.0115 (15)

Geometric parameters (Å, º) top

C1—C2	1.389 (4)	C7—C8ⁱ	1.379 (3)
C1—C6	1.391 (4)	C7—C8	1.379 (3)
C1—N1	1.410 (3)	C7—N1	1.425 (4)
C2—C3	1.376 (4)	C8—C9	1.383 (4)
C2—H1	0.95 (3)	C8—H6	0.93 (3)
C3—C4	1.383 (4)	C9—C10	1.368 (4)
C3—H2	0.88 (3)	C9—H7	0.95 (3)
C4—C5	1.369 (4)	C10—C9ⁱ	1.368 (4)
C4—C11	1.464 (4)	C10—H8	0.95 (5)
C5—C6	1.372 (4)	C11—O1	1.181 (4)
C5—H3	0.96 (3)	C11—H5	1.04 (4)
C6—H4	0.95 (3)	N1—C1ⁱ	1.410 (3)

C2—C1—C6	119.1 (2)	C8ⁱ—C7—C8	119.4 (4)
C2—C1—N1	120.6 (2)	C8ⁱ—C7—N1	120.32 (18)
C6—C1—N1	120.3 (2)	C8—C7—N1	120.32 (18)
C3—C2—C1	119.2 (3)	C7—C8—C9	120.1 (3)
C3—C2—H1	122.3 (16)	C7—C8—H6	117.3 (17)
C1—C2—H1	118.5 (16)	C9—C8—H6	122.6 (17)
C2—C3—C4	121.7 (3)	C10—C9—C8	120.3 (3)
C2—C3—H2	117 (2)	C10—C9—H7	121 (2)
C4—C3—H2	121 (2)	C8—C9—H7	119 (2)
C5—C4—C3	118.4 (3)	C9ⁱ—C10—C9	119.9 (4)
C5—C4—C11	119.3 (3)	C9ⁱ—C10—H8	120.1 (2)
C3—C4—C11	122.2 (3)	C9—C10—H8	120.1 (2)
C4—C5—C6	121.1 (3)	O1—C11—C4	125.8 (4)
C4—C5—H3	115.9 (19)	O1—C11—H5	117 (2)
C6—C5—H3	122.9 (19)	C4—C11—H5	116 (2)
C5—C6—C1	120.3 (3)	C1—N1—C1ⁱ	121.0 (3)
C5—C6—H4	121.0 (16)	C1—N1—C7	119.50 (14)
C1—C6—H4	118.6 (16)	C1ⁱ—N1—C7	119.50 (14)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H3···O1ⁱⁱ	0.96 (3)	2.48 (3)	3.396 (4)	159 (3)
C9—H7···O1ⁱⁱⁱ	0.95 (3)	2.55 (4)	3.495 (4)	173 (3)

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

Experimental details

Crystal data
Chemical formula	C₂₀H₁₅NO₂
M_r	301.33
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	8.836 (2), 9.710 (2), 18.621 (4)
V (Å³)	1597.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.18 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.980, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	7399, 1412, 1087
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.187, 1.07
No. of reflections	1412
No. of parameters	136
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H3···O1ⁱ	0.96 (3)	2.48 (3)	3.396 (4)	159 (3)
C9—H7···O1ⁱⁱ	0.95 (3)	2.55 (4)	3.495 (4)	173 (3)

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

Acknowledgements

The authors thank the Shandong Distinguished Middle-aged and Young Scientist Encouragement and Reward Scheme (No. 2006BS04006) for financial support.

References

Bruker (2000). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Krishnamohan Sharma, C. V. & Desiraju, G. R. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 2345–2352. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thomas, M., Said, G., Mohamed, A., Mireille, B. & Olivier, M. (2005). Synthesis, pp. 1771–1774. Google Scholar