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

Zhang, M.-L.; Yang, J.

doi:10.1107/S1600536810007099

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o727

doi:10.1107/S1600536810007099

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

Mei-Lin Zhang ^a and Jie Yang ^b ^*

^aCollege of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bInstitute of Materials Science & Technology, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: ppsf@scu.edu.cn

(Received 9 February 2010; accepted 24 February 2010; online 3 March 2010)

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

Experimental

Crystal data

C₁₉H₁₃F₂N
M_r = 293.30
Orthorhombic, P b c a
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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.115
S = 0.98
2612 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18⋯F1ⁱ	0.93	2.54	3.379 (2)	150
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT 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: SHELXTL.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

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

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

Crystal data top

C₁₉H₁₃F₂N	F(000) = 1216
M_r = 293.30	D_x = 1.316 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1417 reflections
a = 18.104 (6) Å	θ = 2.4–24.1°
b = 8.612 (3) Å	µ = 0.09 mm⁻¹
c = 18.985 (6) Å	T = 293 K
V = 2960.0 (17) Å³	Plate, yellow
Z = 8	0.40 × 0.27 × 0.11 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	2612 independent reflections
Radiation source: fine-focus sealed tube	2060 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
phi and ω scans	θ_max = 25.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1996)	h = −16→21
T_min = 0.963, T_max = 0.990	k = −10→10
13881 measured reflections	l = −20→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0728P)² + 0.3185P] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
2612 reflections	Δρ_max = 0.15 e Å⁻³
200 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0017 (5)

Crystal data top

C₁₉H₁₃F₂N	V = 2960.0 (17) Å³
M_r = 293.30	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 18.104 (6) Å	µ = 0.09 mm⁻¹
b = 8.612 (3) Å	T = 293 K
c = 18.985 (6) Å	0.40 × 0.27 × 0.11 mm

Data collection top

Bruker APEX CCD area-detector diffractometer	2612 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1996)	2060 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.990	R_int = 0.022
13881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 0.98	Δρ_max = 0.15 e Å⁻³
2612 reflections	Δρ_min = −0.17 e Å⁻³
200 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.20644 (7)	0.24801 (15)	0.27677 (8)	0.0490 (3)
C2	0.26143 (8)	0.25396 (15)	0.33496 (8)	0.0505 (4)
C3	0.33329 (8)	0.20396 (17)	0.32292 (9)	0.0591 (4)
H3	0.3463	0.1672	0.2786	0.071*
C4	0.38557 (10)	0.20799 (19)	0.37563 (10)	0.0676 (5)
H4	0.4335	0.1733	0.3675	0.081*
C5	0.36536 (9)	0.2642 (2)	0.44019 (9)	0.0645 (4)
C6	0.29542 (9)	0.3134 (2)	0.45459 (9)	0.0683 (5)
H6	0.2831	0.3498	0.4992	0.082*
C7	0.24335 (9)	0.30831 (19)	0.40158 (8)	0.0608 (4)
H7	0.1954	0.3418	0.4106	0.073*
C8	0.12682 (7)	0.23425 (15)	0.29640 (7)	0.0463 (3)
C9	0.07420 (8)	0.33442 (17)	0.26868 (8)	0.0538 (4)
H9	0.0887	0.4115	0.2373	0.065*
C10	0.00099 (8)	0.32128 (18)	0.28699 (8)	0.0576 (4)
H10	−0.0340	0.3894	0.2688	0.069*
C11	−0.01927 (8)	0.20545 (17)	0.33273 (8)	0.0527 (4)
C12	0.03040 (8)	0.10401 (17)	0.36102 (8)	0.0559 (4)
H12	0.0151	0.0259	0.3916	0.067*
C13	0.10393 (8)	0.12022 (16)	0.34313 (8)	0.0533 (4)
H13	0.1387	0.0535	0.3628	0.064*
C14	0.18353 (8)	0.22899 (17)	0.15481 (8)	0.0531 (4)
C15	0.16862 (9)	0.35005 (19)	0.10865 (8)	0.0634 (4)
H15	0.1886	0.4479	0.1168	0.076*
C16	0.12419 (10)	0.3250 (2)	0.05081 (9)	0.0710 (5)
H16	0.1133	0.4069	0.0207	0.085*
C17	0.09587 (10)	0.1799 (2)	0.03724 (9)	0.0722 (5)
H17	0.0659	0.1638	−0.0018	0.087*
C18	0.11214 (10)	0.0590 (2)	0.08170 (9)	0.0725 (5)
H18	0.0936	−0.0395	0.0722	0.087*
C19	0.15577 (9)	0.08234 (19)	0.14032 (9)	0.0640 (4)
H19	0.1666	−0.0003	0.1701	0.077*
F1	0.41742 (6)	0.27364 (14)	0.49157 (6)	0.0917 (4)
F2	−0.09151 (5)	0.19054 (12)	0.34959 (5)	0.0732 (3)
N1	0.23085 (7)	0.25324 (14)	0.21332 (7)	0.0575 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0464 (8)	0.0492 (7)	0.0515 (9)	−0.0010 (6)	0.0039 (6)	0.0047 (6)
C2	0.0473 (8)	0.0524 (7)	0.0519 (9)	−0.0050 (6)	0.0023 (6)	0.0062 (6)
C3	0.0527 (9)	0.0633 (9)	0.0614 (10)	0.0036 (7)	0.0011 (7)	0.0018 (7)
C4	0.0535 (9)	0.0703 (10)	0.0790 (13)	0.0052 (7)	−0.0069 (9)	0.0084 (8)
C5	0.0616 (10)	0.0718 (10)	0.0601 (11)	−0.0123 (8)	−0.0132 (8)	0.0184 (8)
C6	0.0669 (11)	0.0877 (11)	0.0504 (9)	−0.0179 (8)	0.0009 (8)	0.0038 (8)
C7	0.0505 (8)	0.0762 (10)	0.0556 (9)	−0.0082 (7)	0.0055 (7)	0.0003 (8)
C8	0.0459 (7)	0.0475 (7)	0.0455 (8)	−0.0007 (6)	0.0010 (6)	−0.0008 (6)
C9	0.0568 (9)	0.0515 (8)	0.0531 (9)	0.0033 (6)	0.0037 (7)	0.0069 (6)
C10	0.0509 (8)	0.0627 (8)	0.0591 (9)	0.0107 (7)	0.0008 (7)	0.0027 (7)
C11	0.0418 (7)	0.0652 (9)	0.0513 (9)	−0.0038 (6)	0.0033 (6)	−0.0098 (7)
C12	0.0544 (8)	0.0589 (8)	0.0543 (9)	−0.0093 (7)	0.0028 (7)	0.0064 (7)
C13	0.0484 (8)	0.0543 (8)	0.0570 (9)	0.0006 (6)	−0.0013 (7)	0.0088 (7)
C14	0.0452 (7)	0.0679 (9)	0.0463 (8)	0.0012 (6)	0.0099 (6)	0.0013 (7)
C15	0.0685 (10)	0.0643 (9)	0.0574 (10)	−0.0017 (7)	0.0046 (8)	0.0061 (8)
C16	0.0723 (11)	0.0837 (12)	0.0571 (10)	0.0078 (9)	0.0012 (9)	0.0122 (9)
C17	0.0640 (10)	0.0992 (13)	0.0534 (10)	−0.0021 (9)	0.0007 (8)	−0.0032 (9)
C18	0.0776 (11)	0.0758 (11)	0.0640 (11)	−0.0118 (9)	0.0051 (9)	−0.0085 (9)
C19	0.0695 (10)	0.0636 (9)	0.0589 (10)	0.0008 (8)	0.0060 (8)	0.0047 (7)
F1	0.0796 (7)	0.1177 (9)	0.0777 (8)	−0.0138 (6)	−0.0290 (6)	0.0189 (6)
F2	0.0456 (5)	0.0960 (7)	0.0778 (7)	−0.0052 (4)	0.0076 (4)	−0.0007 (5)
N1	0.0497 (7)	0.0713 (8)	0.0514 (8)	−0.0028 (6)	0.0052 (6)	0.0058 (6)

Geometric parameters (Å, º) top

C1—N1	1.2839 (19)	C10—H10	0.9300
C1—C2	1.488 (2)	C11—F2	1.3527 (17)
C1—C8	1.494 (2)	C11—C12	1.364 (2)
C2—C7	1.388 (2)	C12—C13	1.381 (2)
C2—C3	1.389 (2)	C12—H12	0.9300
C3—C4	1.378 (2)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.388 (2)
C4—C5	1.368 (3)	C14—C19	1.387 (2)
C4—H4	0.9300	C14—N1	1.418 (2)
C5—F1	1.3589 (19)	C15—C16	1.378 (2)
C5—C6	1.363 (3)	C15—H15	0.9300
C6—C7	1.380 (2)	C16—C17	1.375 (3)
C6—H6	0.9300	C16—H16	0.9300
C7—H7	0.9300	C17—C18	1.373 (3)
C8—C13	1.3868 (19)	C17—H17	0.9300
C8—C9	1.389 (2)	C18—C19	1.379 (2)
C9—C10	1.375 (2)	C18—H18	0.9300
C9—H9	0.9300	C19—H19	0.9300
C10—C11	1.372 (2)

N1—C1—C2	117.71 (13)	C11—C10—H10	120.7
N1—C1—C8	124.69 (13)	F2—C11—C12	118.91 (14)
C2—C1—C8	117.59 (12)	F2—C11—C10	118.50 (13)
C7—C2—C3	118.38 (15)	C12—C11—C10	122.59 (14)
C7—C2—C1	122.04 (14)	C11—C12—C13	118.29 (14)
C3—C2—C1	119.58 (14)	C11—C12—H12	120.9
C4—C3—C2	121.07 (16)	C13—C12—H12	120.9
C4—C3—H3	119.5	C12—C13—C8	121.13 (13)
C2—C3—H3	119.5	C12—C13—H13	119.4
C5—C4—C3	118.42 (16)	C8—C13—H13	119.4
C5—C4—H4	120.8	C15—C14—C19	119.22 (15)
C3—C4—H4	120.8	C15—C14—N1	120.08 (14)
F1—C5—C6	118.79 (17)	C19—C14—N1	120.55 (14)
F1—C5—C4	118.62 (16)	C16—C15—C14	119.91 (16)
C6—C5—C4	122.58 (16)	C16—C15—H15	120.0
C5—C6—C7	118.58 (17)	C14—C15—H15	120.0
C5—C6—H6	120.7	C17—C16—C15	120.63 (17)
C7—C6—H6	120.7	C17—C16—H16	119.7
C6—C7—C2	120.97 (16)	C15—C16—H16	119.7
C6—C7—H7	119.5	C16—C17—C18	119.62 (17)
C2—C7—H7	119.5	C16—C17—H17	120.2
C13—C8—C9	118.51 (13)	C18—C17—H17	120.2
C13—C8—C1	120.28 (12)	C19—C18—C17	120.55 (17)
C9—C8—C1	121.21 (13)	C19—C18—H18	119.7
C10—C9—C8	120.95 (14)	C17—C18—H18	119.7
C10—C9—H9	119.5	C18—C19—C14	120.02 (16)
C8—C9—H9	119.5	C18—C19—H19	120.0
C9—C10—C11	118.51 (13)	C14—C19—H19	120.0
C9—C10—H10	120.7	C1—N1—C14	121.45 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···F1ⁱ	0.93	2.54	3.379 (2)	150

Symmetry code: (i) −x+1/2, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₃F₂N
M_r	293.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	18.104 (6), 8.612 (3), 18.985 (6)
V (Å³)	2960.0 (17)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.27 × 0.11

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1996)
T_min, T_max	0.963, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	13881, 2612, 2060
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.115, 0.98
No. of reflections	2612
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···F1ⁱ	0.93	2.54	3.379 (2)	150

Symmetry code: (i) −x+1/2, −y, z−1/2.

Acknowledgements

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.

References

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