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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o727.
Published online 2010 March 3. doi:  10.1107/S1600536810007099
PMCID: PMC2983916

N-[Bis(4-fluoro­phen­yl)methyl­ene]aniline

Abstract

The title compound, C19H13F2N, was synthesized by an addition reaction of bis­(4-fluoro­phen­yl)methanone with aniline. The dihedral angles formed by the fluoro­benzene rings with the aniline ring are 81.04 (5) and 64.15 (5)°. In the crystal packing, inter­molecular C—H(...)F hydrogen bonds link mol­ecules into zigzag chains parallel to the c axis.

Related literature

For synthetic applications of the title compound, see: Brink et al. (1993 [triangle]); Roovers et al. (1990 [triangle]). For the properties of deriv­atives of the title compound, see: Hedrick et al. (1993 [triangle]); Niswander & Martell (1978 [triangle]); Qi et al. (1999 [triangle]); Bourgeois et al. (1996 [triangle]).

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Object name is e-66-0o727-scheme1.jpg

Experimental

Crystal data

  • C19H13F2N
  • M r = 293.30
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o727-efi1.jpg
  • a = 18.104 (6) Å
  • b = 8.612 (3) Å
  • c = 18.985 (6) Å
  • V = 2960.0 (17) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.40 × 0.27 × 0.11 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1996 [triangle]) T min = 0.963, T max = 0.990
  • 13881 measured reflections
  • 2612 independent reflections
  • 2060 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.115
  • S = 0.98
  • 2612 reflections
  • 200 parameters
  • H-atom parameters constrained
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 1996 [triangle]); cell refinement: SAINT (Bruker, 1996 [triangle]); data reduction: SAINT program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007099/rz2421sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007099/rz2421Isup2.hkl

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

Acknowledgments

The authors thank Mr Ning-Hai Hu of the Chang Chun Institute of Applied Chemistry, Chinese Academy of Sciences, for the X-ray data collection.

supplementary crystallographic information

Comment

The title compound, N-[bis(4-fluorophenyl)methylene]aniline, can be used as the monomer of high performance polyarylene ether ketone (Brink et al., 1993; Roovers et al., 1990). Some derivatives of this compound have been reported with good thermostability and chemical-resistance (Hedrick et al., 1993; Niswander & Martell, 1978; Qi et al., 1999; Bourgeois et al., 1996). We report here the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the C1═N\ bond is 1.2839 (19) Å. The fluorobenzene rings form a dihedral angle of 66.52 (4)° and are oriented with respect to the aniline ring at dihedral angles of 81.04 (5) and 64.15 (5)°. In the crystal packing, intermolecular C—H···F hydrogen bonds (Table 1) link molecules into zig-zag chains parallel to the c axis.

Experimental

General procedure for the synthesis of the title compound: bis(4-fluorophenyl)methanone (21.8 g, 0.10 mol), aniline (9.3 g, 0.10 mol), toluene (500 ml) and p-methylbenzenesulfonic acid (1.7 g, 0.01 mol) were charged into a three-necked round-bottomed flask fitted whith a mechanical stirrer, a nitrogen inlet and a thermometer. The mixture was stirred at 120°C for 2 h, then it was heated to boiling point and kept for 12 h under nitrogen atmosphere. After the reactor was cooled to room temperature, the reaction solution was poured into methanol. The resulting solid was filtered, washed with cold methanol, dried under vacuum to get yellow powder. Yellow crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution at room temperature over a period a week.

Refinement

All the H atoms could be found in the difference Fourier maps. They were positioned geometrically with C—H = 0.93 Å. Uiso(H) = 1.2Ueq (aromatic C) while Uiso(H) = 1.5Ueq (O).

Figures

Fig. 1.
The molecular structure of title compound with displacement ellipsoids drawn at the 50° probability level.

Crystal data

C19H13F2NF(000) = 1216
Mr = 293.30Dx = 1.316 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1417 reflections
a = 18.104 (6) Åθ = 2.4–24.1°
b = 8.612 (3) ŵ = 0.09 mm1
c = 18.985 (6) ÅT = 293 K
V = 2960.0 (17) Å3Plate, yellow
Z = 80.40 × 0.27 × 0.11 mm

Data collection

Bruker APEX CCD area-detector diffractometer2612 independent reflections
Radiation source: fine-focus sealed tube2060 reflections with I > 2σ(I)
graphiteRint = 0.022
phi and ω scansθmax = 25.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1996)h = −16→21
Tmin = 0.963, Tmax = 0.990k = −10→10
13881 measured reflectionsl = −20→22

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.115w = 1/[σ2(Fo2) + (0.0728P)2 + 0.3185P] where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
2612 reflectionsΔρmax = 0.15 e Å3
200 parametersΔρmin = −0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0017 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C10.20644 (7)0.24801 (15)0.27677 (8)0.0490 (3)
C20.26143 (8)0.25396 (15)0.33496 (8)0.0505 (4)
C30.33329 (8)0.20396 (17)0.32292 (9)0.0591 (4)
H30.34630.16720.27860.071*
C40.38557 (10)0.20799 (19)0.37563 (10)0.0676 (5)
H40.43350.17330.36750.081*
C50.36536 (9)0.2642 (2)0.44019 (9)0.0645 (4)
C60.29542 (9)0.3134 (2)0.45459 (9)0.0683 (5)
H60.28310.34980.49920.082*
C70.24335 (9)0.30831 (19)0.40158 (8)0.0608 (4)
H70.19540.34180.41060.073*
C80.12682 (7)0.23425 (15)0.29640 (7)0.0463 (3)
C90.07420 (8)0.33442 (17)0.26868 (8)0.0538 (4)
H90.08870.41150.23730.065*
C100.00099 (8)0.32128 (18)0.28699 (8)0.0576 (4)
H10−0.03400.38940.26880.069*
C11−0.01927 (8)0.20545 (17)0.33273 (8)0.0527 (4)
C120.03040 (8)0.10401 (17)0.36102 (8)0.0559 (4)
H120.01510.02590.39160.067*
C130.10393 (8)0.12022 (16)0.34313 (8)0.0533 (4)
H130.13870.05350.36280.064*
C140.18353 (8)0.22899 (17)0.15481 (8)0.0531 (4)
C150.16862 (9)0.35005 (19)0.10865 (8)0.0634 (4)
H150.18860.44790.11680.076*
C160.12419 (10)0.3250 (2)0.05081 (9)0.0710 (5)
H160.11330.40690.02070.085*
C170.09587 (10)0.1799 (2)0.03724 (9)0.0722 (5)
H170.06590.1638−0.00180.087*
C180.11214 (10)0.0590 (2)0.08170 (9)0.0725 (5)
H180.0936−0.03950.07220.087*
C190.15577 (9)0.08234 (19)0.14032 (9)0.0640 (4)
H190.1666−0.00030.17010.077*
F10.41742 (6)0.27364 (14)0.49157 (6)0.0917 (4)
F2−0.09151 (5)0.19054 (12)0.34959 (5)0.0732 (3)
N10.23085 (7)0.25324 (14)0.21332 (7)0.0575 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0464 (8)0.0492 (7)0.0515 (9)−0.0010 (6)0.0039 (6)0.0047 (6)
C20.0473 (8)0.0524 (7)0.0519 (9)−0.0050 (6)0.0023 (6)0.0062 (6)
C30.0527 (9)0.0633 (9)0.0614 (10)0.0036 (7)0.0011 (7)0.0018 (7)
C40.0535 (9)0.0703 (10)0.0790 (13)0.0052 (7)−0.0069 (9)0.0084 (8)
C50.0616 (10)0.0718 (10)0.0601 (11)−0.0123 (8)−0.0132 (8)0.0184 (8)
C60.0669 (11)0.0877 (11)0.0504 (9)−0.0179 (8)0.0009 (8)0.0038 (8)
C70.0505 (8)0.0762 (10)0.0556 (9)−0.0082 (7)0.0055 (7)0.0003 (8)
C80.0459 (7)0.0475 (7)0.0455 (8)−0.0007 (6)0.0010 (6)−0.0008 (6)
C90.0568 (9)0.0515 (8)0.0531 (9)0.0033 (6)0.0037 (7)0.0069 (6)
C100.0509 (8)0.0627 (8)0.0591 (9)0.0107 (7)0.0008 (7)0.0027 (7)
C110.0418 (7)0.0652 (9)0.0513 (9)−0.0038 (6)0.0033 (6)−0.0098 (7)
C120.0544 (8)0.0589 (8)0.0543 (9)−0.0093 (7)0.0028 (7)0.0064 (7)
C130.0484 (8)0.0543 (8)0.0570 (9)0.0006 (6)−0.0013 (7)0.0088 (7)
C140.0452 (7)0.0679 (9)0.0463 (8)0.0012 (6)0.0099 (6)0.0013 (7)
C150.0685 (10)0.0643 (9)0.0574 (10)−0.0017 (7)0.0046 (8)0.0061 (8)
C160.0723 (11)0.0837 (12)0.0571 (10)0.0078 (9)0.0012 (9)0.0122 (9)
C170.0640 (10)0.0992 (13)0.0534 (10)−0.0021 (9)0.0007 (8)−0.0032 (9)
C180.0776 (11)0.0758 (11)0.0640 (11)−0.0118 (9)0.0051 (9)−0.0085 (9)
C190.0695 (10)0.0636 (9)0.0589 (10)0.0008 (8)0.0060 (8)0.0047 (7)
F10.0796 (7)0.1177 (9)0.0777 (8)−0.0138 (6)−0.0290 (6)0.0189 (6)
F20.0456 (5)0.0960 (7)0.0778 (7)−0.0052 (4)0.0076 (4)−0.0007 (5)
N10.0497 (7)0.0713 (8)0.0514 (8)−0.0028 (6)0.0052 (6)0.0058 (6)

Geometric parameters (Å, °)

C1—N11.2839 (19)C10—H100.9300
C1—C21.488 (2)C11—F21.3527 (17)
C1—C81.494 (2)C11—C121.364 (2)
C2—C71.388 (2)C12—C131.381 (2)
C2—C31.389 (2)C12—H120.9300
C3—C41.378 (2)C13—H130.9300
C3—H30.9300C14—C151.388 (2)
C4—C51.368 (3)C14—C191.387 (2)
C4—H40.9300C14—N11.418 (2)
C5—F11.3589 (19)C15—C161.378 (2)
C5—C61.363 (3)C15—H150.9300
C6—C71.380 (2)C16—C171.375 (3)
C6—H60.9300C16—H160.9300
C7—H70.9300C17—C181.373 (3)
C8—C131.3868 (19)C17—H170.9300
C8—C91.389 (2)C18—C191.379 (2)
C9—C101.375 (2)C18—H180.9300
C9—H90.9300C19—H190.9300
C10—C111.372 (2)
N1—C1—C2117.71 (13)C11—C10—H10120.7
N1—C1—C8124.69 (13)F2—C11—C12118.91 (14)
C2—C1—C8117.59 (12)F2—C11—C10118.50 (13)
C7—C2—C3118.38 (15)C12—C11—C10122.59 (14)
C7—C2—C1122.04 (14)C11—C12—C13118.29 (14)
C3—C2—C1119.58 (14)C11—C12—H12120.9
C4—C3—C2121.07 (16)C13—C12—H12120.9
C4—C3—H3119.5C12—C13—C8121.13 (13)
C2—C3—H3119.5C12—C13—H13119.4
C5—C4—C3118.42 (16)C8—C13—H13119.4
C5—C4—H4120.8C15—C14—C19119.22 (15)
C3—C4—H4120.8C15—C14—N1120.08 (14)
F1—C5—C6118.79 (17)C19—C14—N1120.55 (14)
F1—C5—C4118.62 (16)C16—C15—C14119.91 (16)
C6—C5—C4122.58 (16)C16—C15—H15120.0
C5—C6—C7118.58 (17)C14—C15—H15120.0
C5—C6—H6120.7C17—C16—C15120.63 (17)
C7—C6—H6120.7C17—C16—H16119.7
C6—C7—C2120.97 (16)C15—C16—H16119.7
C6—C7—H7119.5C16—C17—C18119.62 (17)
C2—C7—H7119.5C16—C17—H17120.2
C13—C8—C9118.51 (13)C18—C17—H17120.2
C13—C8—C1120.28 (12)C19—C18—C17120.55 (17)
C9—C8—C1121.21 (13)C19—C18—H18119.7
C10—C9—C8120.95 (14)C17—C18—H18119.7
C10—C9—H9119.5C18—C19—C14120.02 (16)
C8—C9—H9119.5C18—C19—H19120.0
C9—C10—C11118.51 (13)C14—C19—H19120.0
C9—C10—H10120.7C1—N1—C14121.45 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C18—H18···F1i0.932.543.379 (2)150

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2421).

References

  • Bourgeois, J., Devaux, J., Legras, R. & Parsons, W. (1996). Polymer, 37, 3171–3176.
  • Brink, A. E., Lin, M. C. & Riffle, J. S. (1993). Chem. Mater.5, 925–929.
  • Bruker (1996). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hedrick, J. L., Volksen, W. & Mohanty, D. K. (1993). Polym. Bull.30, 33–38.
  • Niswander, R. H. & Martell, A. E. (1978). Inorg. Chem.17, 2341–2344.
  • Qi, Y. H., Chen, T. L. & Xu, J. P. (1999). Polym, Bull.42, 245–249.
  • Roovers, J., Cooney, J. D. & Toporowski, P. M. (1990). Macromolecules, 23, 1611–1618.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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