N,N′-[(2E,3E)-Butane-2,3-diylidene]bis[4-fluoro-2-(1-phenyl­eth­yl)aniline]

Wei, J.; She, H.; Shi, L.; Lei, Z.

doi:10.1107/S1600536814002657

organic compounds

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Volume 70| Part 3| March 2014| Page o275

doi:10.1107/S1600536814002657

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N,N′-[(2E,3E)-Butane-2,3-diylidene]bis[4-fluoro-2-(1-phenylethyl)aniline]

Juanjuan Wei,^a Houde She,^a ^* Lijun Shi ^a and Ziqiang Lei ^a

^aKey Laboratory of Eco-Environment-Related Polymer Materials of the Ministry of, Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: she_houde@163.com

(Received 18 December 2013; accepted 5 February 2014; online 12 February 2014)

The title molecule, C₃₂H₃₀F₂N₂, a product of the condensation reaction of butane-2,3-dione and 4-fluoro-2-(1-phenylethyl)aniline, is located about an inversion centre. In the asymmetric unit, the dihedral angle between the planes of the benzene and phenyl rings is 84.27 (5)°. Neither hydrogen bonding nor aromatic stacking is observed in the crystal structure.

CCDC reference: 985187

Related literature

For the synthesis of α-diimine ligands, see: Grasa et al. (2001 ); Williams et al. (2008 ); Hanhan et al. (2012 ); Partyka (2011 ); Yuan et al. (2012 ). For related structures, see: Zou et al. (2008 ); Lohr et al. (2011 ).

Experimental

Crystal data

C₃₂H₃₀F₂N₂
M_r = 480.58
Monoclinic, P 2₁ /n
a = 11.5335 (11) Å
b = 9.5024 (12) Å
c = 12.1318 (14) Å
β = 91.660 (11)°
V = 1329.0 (3) Å³
Z = 2
Cu Kα radiation
μ = 0.64 mm⁻¹
T = 295 K
0.35 × 0.28 × 0.26 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.808, T_max = 0.852
5982 measured reflections
2507 independent reflections
2132 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.118
S = 1.07
2507 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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

CCDC reference: 985187

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814002657/rk2419sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002657/rk2419Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814002657/rk2419Isup3.cml

checkCIF report

Comment top

An α-diimine ligands with different electronic property, rigidity and steric hindrance has been widely synthesized due to their significant applications in catalysis, coordination chemistry and carbene chemistry (Grasa et al., 2001; Williams et al., 2008; Hanhan et al., 2012; Partyka, 2011; Yuan et al., 2012). As part of our research efforts focused on developing ligands and organic catalysts, a novel series of imine derivatives were synthesized. Herein, we report the preparation and crystal structure of the title compound (Fig. 1).

The title molecule, is a symmetrical structure, and the central butanediimine moiety (N═C(Me)–C(Me)═N) is planar. The dihedral angles between the benzene ring C8-C13 and benzene ring C1-C6 is 84.27 (5)°. The molecular dimensions in the title compound agree very well with the corresponding one reported in a few closely related compounds (Zou et al., 2008; Lohr et al. 2011).

Related literature top

For the synthesis of α-diimine ligands, see: Grasa et al. (2001); Williams et al. (2008); Hanhan et al. (2012); Partyka (2011); Yuan et al. (2012). For related structures, see: Zou et al. (2008); Lohr et al. (2011).

Experimental top

Formic acid (1.0 ml) was added to a stirred solution of 4-fluoro-2-(1-phenylethyl)aniline (1.5 mmol) and 2,3-butanedione (0.7 mmol) in 20 ml anhydrous methanol (20 ml). The mixture was stirred at 323 K for 24 h, then cooled, and the precipitate was separated by filtration. The solid was recrystallized from ethanol/dichloromethane (v/v = 12:1), washed with cold ethanol and dried under vacuum to give the title compound (Fig. 2). Yield is 82%. Crystals suitable for X-ray diffraction were grown in cyclohexane/dichloromethane (v/v = 1:2) solution at room temperature by the slow evaporation method. ¹H NMR (400 MHz, CDCl₃): δ (p.p.m.) 7.19(t, J = 7.4 Hz, 4H), 7.09-7.13 (m, 4H), 7.01-7.05(m, 4H), 6.93 (dt, J = 8.4, 2.9 Hz, 2H), 6.47 (dd, J = 8.6, 5.3 Hz, 2H), 4.08 (q, J = 6.8 Hz, 2H), 1.62 (s, 6H), 1.56 (d, J = 7.2 Hz, 6H). ¹³C NMR (100 MHz, CDCl₃): δ (p.p.m.) 168.54, 161.22, 158.82, 145.58, 144.69, 137.34, 128.31, 127.57, 126.06, 118.94, 113.58, 40.17, 21.42, 20.86.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 molecule with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level. Symmetry code: (i) -x+1, -y+1, -z+1.
	Fig. 2. A condensation reaction of 2,3-butanedione and 4-fluoro-2-(1-phenylethyl)aniline.

N,N'-[(2E,3E)-Butane-2,3-diylidene]bis[4-fluoro-2-(1-phenylethyl)aniline] top

Crystal data top

C₃₂H₃₀F₂N₂	F(000) = 508
M_r = 480.58	D_x = 1.201 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 11.5335 (11) Å	Cell parameters from 2620 reflections
b = 9.5024 (12) Å	θ = 5.2–70.8°
c = 12.1318 (14) Å	µ = 0.64 mm⁻¹
β = 91.660 (11)°	T = 295 K
V = 1329.0 (3) Å³	Block, clear light yellow
Z = 2	0.35 × 0.28 × 0.26 mm

Data collection top

Bruker APEXII CCD diffractometer	2507 independent reflections
Radiation source: fine-focus sealed tube	2132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 70.5°, θ_min = 5.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→12
T_min = 0.808, T_max = 0.852	k = −11→10
5982 measured reflections	l = −14→14

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.056P)² + 0.1881P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2507 reflections	Δρ_max = 0.18 e Å⁻³
166 parameters	Δρ_min = −0.15 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: 0.0100 (10)

Crystal data top

C₃₂H₃₀F₂N₂	V = 1329.0 (3) Å³
M_r = 480.58	Z = 2
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.5335 (11) Å	µ = 0.64 mm⁻¹
b = 9.5024 (12) Å	T = 295 K
c = 12.1318 (14) Å	0.35 × 0.28 × 0.26 mm
β = 91.660 (11)°

Data collection top

Bruker APEXII CCD diffractometer	2507 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2132 reflections with I > 2σ(I)
T_min = 0.808, T_max = 0.852	R_int = 0.019
5982 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.07	Δρ_max = 0.18 e Å⁻³
2507 reflections	Δρ_min = −0.15 e Å⁻³
166 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
N1	0.37261 (9)	0.49441 (12)	0.57384 (9)	0.0406 (3)
F1	−0.02542 (7)	0.78857 (12)	0.66670 (9)	0.0687 (3)
C1	0.57482 (13)	0.64883 (19)	0.75155 (16)	0.0602 (4)
H1	0.5841	0.5539	0.7683	0.072*
C2	0.67019 (14)	0.7270 (2)	0.72255 (19)	0.0747 (6)
H2	0.7426	0.6844	0.7197	0.090*
C3	0.65862 (15)	0.8671 (2)	0.69791 (18)	0.0743 (6)
H3	0.7224	0.9194	0.6769	0.089*
C4	0.55119 (15)	0.9295 (2)	0.70466 (16)	0.0687 (5)
H4	0.5430	1.0251	0.6899	0.082*
C5	0.45519 (13)	0.85116 (16)	0.73331 (14)	0.0543 (4)
H5	0.3832	0.8946	0.7371	0.065*
C6	0.46540 (11)	0.70923 (15)	0.75624 (11)	0.0420 (3)
C7	0.36098 (11)	0.61988 (15)	0.78526 (11)	0.0419 (3)
H7	0.3860	0.5215	0.7814	0.050*
C8	0.26187 (10)	0.63660 (13)	0.70095 (10)	0.0361 (3)
C9	0.16094 (11)	0.71082 (15)	0.72229 (11)	0.0422 (3)
H9	0.1525	0.7555	0.7898	0.051*
C10	0.07376 (11)	0.71744 (15)	0.64271 (13)	0.0468 (3)
C11	0.08083 (12)	0.65451 (17)	0.54169 (13)	0.0518 (4)
H11	0.0199	0.6601	0.4899	0.062*
C12	0.18142 (12)	0.58231 (17)	0.51907 (11)	0.0488 (4)
H12	0.1885	0.5385	0.4510	0.059*
C13	0.27209 (11)	0.57440 (14)	0.59672 (10)	0.0379 (3)
C14	0.32418 (14)	0.6453 (2)	0.90437 (13)	0.0628 (5)
H14A	0.3068	0.7433	0.9142	0.094*
H14B	0.3862	0.6185	0.9545	0.094*
H14C	0.2566	0.5902	0.9188	0.094*
C15	0.44839 (10)	0.54573 (14)	0.51063 (10)	0.0399 (3)
C16	0.44521 (14)	0.68862 (16)	0.45826 (14)	0.0558 (4)
H16A	0.3815	0.7414	0.4862	0.084*
H16B	0.4356	0.6788	0.3798	0.084*
H16C	0.5165	0.7371	0.4753	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0385 (6)	0.0450 (6)	0.0388 (6)	0.0027 (5)	0.0096 (4)	−0.0018 (5)
F1	0.0418 (5)	0.0843 (7)	0.0801 (7)	0.0223 (4)	0.0027 (4)	−0.0130 (5)
C1	0.0394 (7)	0.0582 (10)	0.0828 (11)	0.0038 (7)	−0.0031 (7)	−0.0062 (8)
C2	0.0369 (8)	0.0801 (13)	0.1072 (16)	−0.0020 (8)	0.0043 (9)	−0.0174 (11)
C3	0.0512 (9)	0.0828 (13)	0.0896 (13)	−0.0260 (9)	0.0173 (9)	−0.0201 (11)
C4	0.0681 (11)	0.0520 (10)	0.0868 (13)	−0.0131 (8)	0.0148 (10)	−0.0048 (8)
C5	0.0465 (8)	0.0472 (8)	0.0698 (10)	0.0001 (6)	0.0093 (7)	−0.0048 (7)
C6	0.0372 (6)	0.0461 (8)	0.0427 (7)	−0.0009 (5)	−0.0001 (5)	−0.0071 (6)
C7	0.0396 (7)	0.0438 (7)	0.0423 (7)	−0.0011 (5)	0.0004 (5)	0.0002 (6)
C8	0.0328 (6)	0.0381 (7)	0.0377 (6)	−0.0033 (5)	0.0066 (5)	−0.0001 (5)
C9	0.0387 (6)	0.0454 (7)	0.0431 (7)	0.0000 (5)	0.0085 (5)	−0.0065 (5)
C10	0.0341 (6)	0.0484 (8)	0.0583 (8)	0.0063 (5)	0.0066 (6)	−0.0022 (6)
C11	0.0407 (7)	0.0626 (9)	0.0515 (8)	0.0045 (6)	−0.0070 (6)	−0.0020 (7)
C12	0.0481 (8)	0.0597 (9)	0.0386 (7)	0.0038 (6)	0.0011 (6)	−0.0071 (6)
C13	0.0353 (6)	0.0406 (7)	0.0383 (6)	0.0003 (5)	0.0087 (5)	0.0010 (5)
C14	0.0585 (9)	0.0879 (13)	0.0420 (8)	−0.0129 (9)	0.0003 (7)	0.0006 (8)
C15	0.0411 (7)	0.0427 (7)	0.0363 (6)	0.0042 (6)	0.0088 (5)	−0.0019 (5)
C16	0.0559 (8)	0.0505 (9)	0.0623 (9)	0.0119 (7)	0.0237 (7)	0.0108 (7)

Geometric parameters (Å, º) top

N1—C15	1.2761 (16)	C8—C9	1.3917 (17)
N1—C13	1.4204 (15)	C8—C13	1.4039 (17)
F1—C10	1.3673 (15)	C9—C10	1.375 (2)
C1—C2	1.382 (2)	C9—H9	0.9300
C1—C6	1.3890 (19)	C10—C11	1.368 (2)
C1—H1	0.9300	C11—C12	1.382 (2)
C2—C3	1.370 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.3892 (19)
C3—C4	1.378 (3)	C12—H12	0.9300
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.387 (2)	C14—H14B	0.9600
C4—H4	0.9300	C14—H14C	0.9600
C5—C6	1.381 (2)	C15—C16	1.4992 (19)
C5—H5	0.9300	C15—C15ⁱ	1.502 (2)
C6—C7	1.5231 (18)	C16—H16A	0.9600
C7—C8	1.5200 (18)	C16—H16B	0.9600
C7—C14	1.537 (2)	C16—H16C	0.9600
C7—H7	0.9800

C15—N1—C13	119.34 (11)	C10—C9—H9	120.3
C2—C1—C6	121.28 (17)	C8—C9—H9	120.3
C2—C1—H1	119.4	F1—C10—C11	118.60 (13)
C6—C1—H1	119.4	F1—C10—C9	118.19 (13)
C3—C2—C1	120.33 (16)	C11—C10—C9	123.20 (12)
C3—C2—H2	119.8	C10—C11—C12	117.84 (13)
C1—C2—H2	119.8	C10—C11—H11	121.1
C2—C3—C4	119.17 (16)	C12—C11—H11	121.1
C2—C3—H3	120.4	C11—C12—C13	120.79 (13)
C4—C3—H3	120.4	C11—C12—H12	119.6
C3—C4—C5	120.61 (17)	C13—C12—H12	119.6
C3—C4—H4	119.7	C12—C13—C8	120.45 (12)
C5—C4—H4	119.7	C12—C13—N1	119.94 (12)
C6—C5—C4	120.71 (15)	C8—C13—N1	119.45 (11)
C6—C5—H5	119.6	C7—C14—H14A	109.5
C4—C5—H5	119.6	C7—C14—H14B	109.5
C5—C6—C1	117.87 (14)	H14A—C14—H14B	109.5
C5—C6—C7	121.83 (12)	C7—C14—H14C	109.5
C1—C6—C7	120.30 (13)	H14A—C14—H14C	109.5
C8—C7—C6	111.74 (11)	H14B—C14—H14C	109.5
C8—C7—C14	113.17 (12)	N1—C15—C16	126.30 (12)
C6—C7—C14	111.80 (12)	N1—C15—C15ⁱ	116.24 (15)
C8—C7—H7	106.5	C16—C15—C15ⁱ	117.44 (14)
C6—C7—H7	106.5	C15—C16—H16A	109.5
C14—C7—H7	106.5	C15—C16—H16B	109.5
C9—C8—C13	118.26 (12)	H16A—C16—H16B	109.5
C9—C8—C7	122.99 (12)	C15—C16—H16C	109.5
C13—C8—C7	118.74 (11)	H16A—C16—H16C	109.5
C10—C9—C8	119.41 (12)	H16B—C16—H16C	109.5

C6—C1—C2—C3	0.2 (3)	C7—C8—C9—C10	−178.02 (13)
C1—C2—C3—C4	1.3 (3)	C8—C9—C10—F1	178.66 (12)
C2—C3—C4—C5	−1.6 (3)	C8—C9—C10—C11	−0.3 (2)
C3—C4—C5—C6	0.4 (3)	F1—C10—C11—C12	−179.60 (13)
C4—C5—C6—C1	1.1 (2)	C9—C10—C11—C12	−0.7 (2)
C4—C5—C6—C7	−178.53 (14)	C10—C11—C12—C13	0.0 (2)
C2—C1—C6—C5	−1.4 (2)	C11—C12—C13—C8	1.7 (2)
C2—C1—C6—C7	178.26 (16)	C11—C12—C13—N1	177.16 (13)
C5—C6—C7—C8	51.52 (17)	C9—C8—C13—C12	−2.62 (19)
C1—C6—C7—C8	−128.13 (14)	C7—C8—C13—C12	177.29 (12)
C5—C6—C7—C14	−76.48 (18)	C9—C8—C13—N1	−178.09 (11)
C1—C6—C7—C14	103.86 (17)	C7—C8—C13—N1	1.83 (18)
C6—C7—C8—C9	−107.17 (14)	C15—N1—C13—C12	77.96 (17)
C14—C7—C8—C9	20.09 (19)	C15—N1—C13—C8	−106.56 (14)
C6—C7—C8—C13	72.91 (15)	C13—N1—C15—C16	2.1 (2)
C14—C7—C8—C13	−159.82 (13)	C13—N1—C15—C15ⁱ	−179.36 (13)
C13—C8—C9—C10	1.89 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₃₂H₃₀F₂N₂
M_r	480.58
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	11.5335 (11), 9.5024 (12), 12.1318 (14)
β (°)	91.660 (11)
V (Å³)	1329.0 (3)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.35 × 0.28 × 0.26

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.808, 0.852
No. of measured, independent and observed [I > 2σ(I)] reflections	5982, 2507, 2132
R_int	0.019

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 1.07
No. of reflections	2507
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge the Natural Science Foundation of China (21261021), the Program for Changjiang Scholars and Innovative Research Teams in Universities of the Ministry of Education of China (IRT1177), the Natural Science Foundation of Gansu Province (1208RJZA140) and the NWNU Young Teachers Reseach Improving Program (NWNU-LKQN-10-11) for financial support.

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