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Acta Cryst. (2009). E65, o2192    [ doi:10.1107/S1600536809031924 ]

4,4'-(Phenylimino)dibenzaldehyde

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

Abstract top

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.

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%.

Refinement top

All the H atoms were located in the difference Fourier map and all parameters are refined independently.

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
[Figure 1] 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.
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis.
4,4'-(Phenylimino)dibenzaldehyde top
Crystal data top
C20H15NO2Dx = 1.253 Mg m−3
Mr = 301.33Melting point = 417–419 K
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 378 reflections
a = 8.836 (2) Åθ = 1.7–25.0°
b = 9.710 (2) ŵ = 0.08 mm−1
c = 18.621 (4) ÅT = 298 K
V = 1597.6 (6) Å3Block, yellow
Z = 40.32 × 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 tube1087 reflections with I > 2σ(I)
graphiteRint = 0.043
π and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −10→10
Tmin = 0.980, Tmax = 0.992k = −11→8
7399 measured reflectionsl = −22→21
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)] = 0.064Hydrogen site location: difference Fourier map
wR(F2) = 0.187All H-atom parameters refined
S = 1.07 w = 1/[σ2(Fo2) + (0.0996P)2 + 0.4228P]
where P = (Fo2 + 2Fc2)/3
1412 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.28 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
C20H15NO2V = 1597.6 (6) Å3
Mr = 301.33Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 8.836 (2) ŵ = 0.08 mm−1
b = 9.710 (2) ÅT = 298 K
c = 18.621 (4) Å0.32 × 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)
Tmin = 0.980, Tmax = 0.992Rint = 0.043
7399 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.064All H-atom parameters refined
wR(F2) = 0.187Δρmax = 0.28 e Å−3
S = 1.07Δρmin = −0.30 e Å−3
1412 reflectionsAbsolute structure: ?
136 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 > 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
C10.0438 (3)0.5517 (3)0.31252 (11)0.0446 (6)
C20.1601 (3)0.6013 (3)0.35553 (15)0.0587 (8)
C30.1977 (4)0.5311 (3)0.41719 (16)0.0670 (9)
C40.1216 (3)0.4133 (3)0.43801 (13)0.0593 (8)
C50.0081 (3)0.3648 (3)0.39479 (14)0.0573 (7)
C6−0.0305 (3)0.4314 (3)0.33246 (13)0.0499 (7)
C70.00000.7700 (3)0.25000.0458 (8)
C80.0651 (3)0.8417 (3)0.19405 (15)0.0581 (8)
C90.0634 (4)0.9841 (3)0.19400 (18)0.0697 (9)
C100.00001.0547 (5)0.25000.0712 (12)
C110.1559 (5)0.3415 (4)0.50518 (16)0.0873 (12)
N10.00000.6232 (3)0.25000.0528 (8)
O10.2531 (4)0.3709 (3)0.54591 (13)0.1245 (12)
H10.212 (3)0.682 (3)0.3407 (14)0.067 (8)*
H20.271 (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)*
H50.101 (4)0.248 (5)0.5133 (19)0.113 (13)*
H60.106 (3)0.790 (3)0.1563 (16)0.071 (8)*
H70.110 (3)1.031 (3)0.1554 (18)0.088 (10)*
H80.00001.153 (6)0.25000.092 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0513 (14)0.0464 (14)0.0362 (12)0.0041 (11)−0.0018 (10)−0.0007 (10)
C20.0626 (17)0.0572 (17)0.0563 (16)−0.0078 (14)−0.0105 (13)−0.0025 (14)
C30.0714 (19)0.073 (2)0.0566 (17)0.0136 (16)−0.0257 (15)−0.0160 (16)
C40.086 (2)0.0492 (15)0.0429 (14)0.0234 (14)−0.0042 (14)−0.0046 (12)
C50.0769 (19)0.0508 (16)0.0441 (14)0.0065 (14)0.0073 (14)0.0005 (12)
C60.0540 (15)0.0510 (15)0.0447 (13)−0.0005 (12)−0.0015 (12)−0.0007 (12)
C70.0535 (19)0.0444 (19)0.0396 (17)0.000−0.0017 (15)0.000
C80.0658 (17)0.0573 (18)0.0513 (15)0.0000 (13)0.0066 (13)0.0003 (13)
C90.081 (2)0.0585 (19)0.0696 (19)−0.0096 (15)0.0021 (16)0.0158 (16)
C100.080 (3)0.044 (2)0.090 (3)0.000−0.005 (2)0.000
C110.138 (3)0.077 (2)0.0460 (17)0.045 (2)−0.017 (2)−0.0119 (17)
N10.072 (2)0.0447 (17)0.0419 (15)0.000−0.0079 (14)0.000
O10.181 (3)0.117 (2)0.0762 (16)0.059 (2)−0.0570 (19)−0.0115 (15)
Geometric parameters (Å, °) top
C1—C21.389 (4)C7—C8i1.379 (3)
C1—C61.391 (4)C7—C81.379 (3)
C1—N11.410 (3)C7—N11.425 (4)
C2—C31.376 (4)C8—C91.383 (4)
C2—H10.95 (3)C8—H60.93 (3)
C3—C41.383 (4)C9—C101.368 (4)
C3—H20.88 (3)C9—H70.95 (3)
C4—C51.369 (4)C10—C9i1.368 (4)
C4—C111.464 (4)C10—H80.95 (5)
C5—C61.372 (4)C11—O11.181 (4)
C5—H30.96 (3)C11—H51.04 (4)
C6—H40.95 (3)N1—C1i1.410 (3)
C2—C1—C6119.1 (2)C8i—C7—C8119.4 (4)
C2—C1—N1120.6 (2)C8i—C7—N1120.32 (18)
C6—C1—N1120.3 (2)C8—C7—N1120.32 (18)
C3—C2—C1119.2 (3)C7—C8—C9120.1 (3)
C3—C2—H1122.3 (16)C7—C8—H6117.3 (17)
C1—C2—H1118.5 (16)C9—C8—H6122.6 (17)
C2—C3—C4121.7 (3)C10—C9—C8120.3 (3)
C2—C3—H2117 (2)C10—C9—H7121 (2)
C4—C3—H2121 (2)C8—C9—H7119 (2)
C5—C4—C3118.4 (3)C9i—C10—C9119.9 (4)
C5—C4—C11119.3 (3)C9i—C10—H8120.1 (2)
C3—C4—C11122.2 (3)C9—C10—H8120.1 (2)
C4—C5—C6121.1 (3)O1—C11—C4125.8 (4)
C4—C5—H3115.9 (19)O1—C11—H5117 (2)
C6—C5—H3122.9 (19)C4—C11—H5116 (2)
C5—C6—C1120.3 (3)C1—N1—C1i121.0 (3)
C5—C6—H4121.0 (16)C1—N1—C7119.50 (14)
C1—C6—H4118.6 (16)C1i—N1—C7119.50 (14)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H3···O1ii0.96 (3)2.48 (3)3.396 (4)159 (3)
C9—H7···O1iii0.95 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H3···O1i0.96 (3)2.48 (3)3.396 (4)159 (3)
C9—H7···O1ii0.95 (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 top

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

references
References top

Bruker (2000). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Krishnamohan Sharma, C. V. & Desiraju, G. R. (1994). J. Chem. Soc. Perkin Trans. 2, pp. 2345–2352.

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

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Thomas, M., Said, G., Mohamed, A., Mireille, B. & Olivier, M. (2005). Synthesis, pp. 1771–1774.