N-[(E)-4-Fluoro­benzyl­idene]-3,4-di­methyl­aniline

Jin, Y.-B.; Chang, Y.-K.; Zhang, Y.; Lei, K.-W.

doi:10.1107/S1600536812030474

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2415

https://doi.org/10.1107/S1600536812030474

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N-[(E)-4-Fluorobenzylidene]-3,4-dimethylaniline

Yue-Bao Jin,^a Yong-Kang Chang,^a Ying Zhang ^a and Ke-Wei Lei ^a ^*

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
^*Correspondence e-mail: leikeweipublic@hotmail.com

(Received 22 May 2012; accepted 4 July 2012; online 10 July 2012)

In the title Schiff base, C₁₅H₁₄FN, the N=C bond length of 1.263 (2) Å is shorter than the N—C bond [1.426 (2) Å], indicating a typical imine double bond. Moreover, the C—N—C angle is 118.5 (2)°. The benzene rings form a dihedral angle of 51.22 (5)°.

Related literature

For general background on the use of Schiff bases as ligands in inorganic and organometallic chemistry, see: Xia et al. (2009 ); Harries & Orford (1983 ); Rodriguez de Barbarin et al. (1994 ). For similar structures, see: Xia et al. (2009); Lindeman et al. (1981 ). For a related synthetic procedure, see: Chen et al. (2005 ).

Experimental

Crystal data

C₁₅H₁₄FN
M_r = 227.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.7487 (3) Å
b = 11.3404 (3) Å
c = 14.2969 (4) Å
V = 1256.31 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.42 × 0.21 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.978, T_max = 0.988
10903 measured reflections
1941 independent reflections
1476 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.103
S = 1.05
1941 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812030474/im2381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030474/im2381Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812030474/im2381Isup3.cml

checkCIF report

Comment top

Schiff bases are among the most useful ligands in coordination chemistry as they readily form stable complexes with most transition metals (Xia et al., 2009; Harries & Orford, 1983; Rodriguez de Barbarin et al., 1994).

The molecular structure of the title compound is illustrated in Fig. 1. Bond angles and bond lengths are within normal ranges. The F1—C13 bond length is 1.361 (2) Å. The N1=C7 bond length of 1.263 (2) Å is shorter than the N1—C1 bond [1.426 (2) Å], indicating a typical imine double bond. Moreover, the C1—N1—C7 bond angle is 118.5 (2)°. The two benzene rings form a dihedral angle of 51.22 (5)° (Xia et al., 2009; Lindeman et al., 1981).

Related literature top

For general background on the use of Schiff bases as ligands in inorganic and organometallic chemistry, see: Xia et al. (2009); Harries & Orford (1983); Rodriguez de Barbarin et al. (1994). For similar structures, see: Xia et al. (2009); Lindeman et al. (1981). For a related synthetic method, see: Chen et al. (2005).

Experimental top

4-Fluorobenzaldehyde (20 mmol, 2.48 g) and 3,4-dimethylbenzenamine (20 mmol, 2.42 g) were dissolved in ethanol and the solution was refluxed for 1 h in a round bottom flask according to a procedure of Chen et al. (2005). After evaporation of the solvent the crude product was recrystallized twice from methanol to give a pure yellow product (yield: 82.5%). Elemental analysis calcd. for C₁₅H₁₄FN: C, 79.29; H, 6.21; N, 6.16; Found: C, 79.25; H, 6.22; N, 6.18%.

Structure description top

For general background on the use of Schiff bases as ligands in inorganic and organometallic chemistry, see: Xia et al. (2009); Harries & Orford (1983); Rodriguez de Barbarin et al. (1994). For similar structures, see: Xia et al. (2009); Lindeman et al. (1981). For a related synthetic method, see: Chen et al. (2005).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound showing displacement ellipsoids on the 30% probability level.

N-[(E)-4-Fluorobenzylidene]-3,4-dimethylaniline top

Crystal data top

C₁₅H₁₄FN	F(000) = 480
M_r = 227.27	D_x = 1.202 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4863 reflections
a = 7.7487 (3) Å	θ = 1.0–29.1°
b = 11.3404 (3) Å	µ = 0.08 mm⁻¹
c = 14.2969 (4) Å	T = 293 K
V = 1256.31 (7) Å³	Block, yellow
Z = 4	0.42 × 0.21 × 0.16 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1941 independent reflections
Radiation source: fine-focus sealed tube	1476 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 29.1°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→10
T_min = 0.978, T_max = 0.988	k = −14→14
10903 measured reflections	l = −18→18

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0515P)² + 0.1023P] where P = (F_o² + 2F_c²)/3
1941 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.10 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₅H₁₄FN	V = 1256.31 (7) Å³
M_r = 227.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.7487 (3) Å	µ = 0.08 mm⁻¹
b = 11.3404 (3) Å	T = 293 K
c = 14.2969 (4) Å	0.42 × 0.21 × 0.16 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1941 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1476 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.988	R_int = 0.023
10903 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.05	Δρ_max = 0.10 e Å⁻³
1941 reflections	Δρ_min = −0.15 e Å⁻³
154 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
N1	0.5157 (2)	0.33118 (14)	0.66820 (10)	0.0529 (4)
F1	0.3419 (2)	0.37162 (14)	1.10226 (9)	0.0933 (5)
C6	0.5091 (2)	0.27263 (16)	0.50536 (13)	0.0487 (4)
H3A	0.4576	0.2024	0.5241	0.058*
C1	0.5509 (2)	0.35665 (15)	0.57238 (12)	0.0472 (4)
C10	0.4210 (2)	0.39849 (16)	0.81944 (13)	0.0502 (4)
C4	0.6225 (2)	0.39542 (17)	0.38272 (12)	0.0503 (4)
C12	0.4505 (3)	0.28949 (19)	0.96341 (15)	0.0638 (5)
H7A	0.4877	0.2234	0.9962	0.077*
C7	0.4517 (2)	0.41157 (16)	0.71858 (13)	0.0517 (4)
H8A	0.4225	0.4827	0.6904	0.062*
C5	0.5424 (2)	0.29105 (16)	0.41079 (12)	0.0488 (4)
C15	0.3412 (3)	0.48874 (18)	0.86852 (14)	0.0636 (5)
H10A	0.3062	0.5563	0.8368	0.076*
C2	0.6304 (2)	0.46021 (16)	0.54411 (13)	0.0534 (4)
H11A	0.6600	0.5173	0.5880	0.064*
C14	0.3125 (3)	0.4801 (2)	0.96400 (16)	0.0696 (6)
H12A	0.2571	0.5401	0.9967	0.083*
C9	0.6641 (3)	0.4191 (2)	0.28139 (13)	0.0715 (6)
H13A	0.7189	0.4948	0.2758	0.107*
H13B	0.5596	0.4187	0.2454	0.107*
H13C	0.7405	0.3591	0.2585	0.107*
C13	0.3683 (3)	0.3808 (2)	1.00840 (13)	0.0629 (6)
C11	0.4761 (3)	0.29881 (17)	0.86783 (13)	0.0571 (5)
H15A	0.5306	0.2380	0.8357	0.068*
C3	0.6656 (2)	0.47809 (16)	0.45035 (13)	0.0547 (4)
H16A	0.7197	0.5476	0.4321	0.066*
C8	0.4925 (3)	0.19754 (19)	0.34034 (14)	0.0686 (6)
H17A	0.4392	0.1325	0.3721	0.103*
H17B	0.5939	0.1705	0.3082	0.103*
H17C	0.4129	0.2303	0.2959	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0567 (9)	0.0536 (8)	0.0484 (8)	−0.0007 (8)	0.0001 (7)	0.0004 (6)
F1	0.1076 (11)	0.1181 (12)	0.0544 (7)	−0.0131 (10)	0.0177 (8)	−0.0034 (7)
C6	0.0467 (9)	0.0448 (9)	0.0546 (10)	−0.0030 (8)	0.0043 (8)	0.0006 (7)
C1	0.0444 (9)	0.0478 (9)	0.0495 (9)	0.0035 (7)	−0.0015 (8)	0.0031 (7)
C10	0.0439 (9)	0.0534 (9)	0.0532 (10)	−0.0025 (8)	−0.0008 (8)	−0.0032 (8)
C4	0.0431 (9)	0.0556 (10)	0.0521 (10)	0.0019 (8)	−0.0011 (8)	0.0055 (8)
C12	0.0736 (13)	0.0594 (11)	0.0584 (11)	−0.0070 (11)	−0.0023 (11)	0.0069 (9)
C7	0.0494 (10)	0.0533 (10)	0.0525 (10)	0.0010 (8)	−0.0048 (8)	0.0036 (8)
C5	0.0407 (9)	0.0535 (10)	0.0521 (10)	0.0003 (8)	0.0012 (8)	−0.0025 (8)
C15	0.0624 (12)	0.0614 (11)	0.0669 (12)	0.0131 (11)	0.0063 (11)	−0.0003 (10)
C2	0.0556 (11)	0.0486 (9)	0.0560 (10)	−0.0047 (8)	−0.0050 (9)	−0.0011 (8)
C14	0.0643 (12)	0.0753 (13)	0.0691 (13)	0.0067 (12)	0.0145 (11)	−0.0122 (11)
C9	0.0788 (14)	0.0785 (14)	0.0573 (12)	−0.0087 (13)	0.0069 (12)	0.0099 (10)
C13	0.0626 (12)	0.0767 (14)	0.0492 (10)	−0.0163 (12)	0.0079 (10)	−0.0067 (9)
C11	0.0664 (12)	0.0501 (9)	0.0548 (10)	−0.0025 (10)	0.0011 (10)	−0.0039 (8)
C3	0.0549 (10)	0.0489 (9)	0.0601 (10)	−0.0072 (9)	−0.0002 (10)	0.0062 (8)
C8	0.0717 (14)	0.0724 (13)	0.0616 (12)	−0.0123 (11)	0.0099 (11)	−0.0150 (10)

Geometric parameters (Å, º) top

N1—C7	1.263 (2)	C7—H8A	0.9300
N1—C1	1.426 (2)	C5—C8	1.513 (3)
F1—C13	1.361 (2)	C15—C14	1.386 (3)
C6—C1	1.390 (3)	C15—H10A	0.9300
C6—C5	1.392 (2)	C2—C3	1.383 (3)
C6—H3A	0.9300	C2—H11A	0.9300
C1—C2	1.386 (2)	C14—C13	1.364 (3)
C10—C15	1.387 (3)	C14—H12A	0.9300
C10—C11	1.392 (3)	C9—H13A	0.9600
C10—C7	1.469 (2)	C9—H13B	0.9600
C4—C3	1.387 (3)	C9—H13C	0.9600
C4—C5	1.395 (2)	C11—H15A	0.9300
C4—C9	1.508 (2)	C3—H16A	0.9300
C12—C13	1.375 (3)	C8—H17A	0.9600
C12—C11	1.385 (3)	C8—H17B	0.9600
C12—H7A	0.9300	C8—H17C	0.9600

C7—N1—C1	118.46 (16)	C3—C2—H11A	120.2
C1—C6—C5	121.56 (16)	C1—C2—H11A	120.2
C1—C6—H3A	119.2	C13—C14—C15	117.8 (2)
C5—C6—H3A	119.2	C13—C14—H12A	121.1
C2—C1—C6	118.92 (17)	C15—C14—H12A	121.1
C2—C1—N1	122.44 (16)	C4—C9—H13A	109.5
C6—C1—N1	118.60 (16)	C4—C9—H13B	109.5
C15—C10—C11	118.99 (18)	H13A—C9—H13B	109.5
C15—C10—C7	119.64 (18)	C4—C9—H13C	109.5
C11—C10—C7	121.33 (17)	H13A—C9—H13C	109.5
C3—C4—C5	118.67 (16)	H13B—C9—H13C	109.5
C3—C4—C9	119.82 (17)	F1—C13—C14	118.3 (2)
C5—C4—C9	121.51 (17)	F1—C13—C12	118.2 (2)
C13—C12—C11	118.1 (2)	C14—C13—C12	123.44 (19)
C13—C12—H7A	121.0	C12—C11—C10	120.55 (19)
C11—C12—H7A	121.0	C12—C11—H15A	119.7
N1—C7—C10	123.40 (17)	C10—C11—H15A	119.7
N1—C7—H8A	118.3	C2—C3—C4	121.94 (17)
C10—C7—H8A	118.3	C2—C3—H16A	119.0
C6—C5—C4	119.28 (16)	C4—C3—H16A	119.0
C6—C5—C8	119.61 (17)	C5—C8—H17A	109.5
C4—C5—C8	121.11 (17)	C5—C8—H17B	109.5
C14—C15—C10	121.2 (2)	H17A—C8—H17B	109.5
C14—C15—H10A	119.4	C5—C8—H17C	109.5
C10—C15—H10A	119.4	H17A—C8—H17C	109.5
C3—C2—C1	119.62 (17)	H17B—C8—H17C	109.5

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄FN
M_r	227.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.7487 (3), 11.3404 (3), 14.2969 (4)
V (Å³)	1256.31 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.42 × 0.21 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.978, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	10903, 1941, 1476
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.103, 1.05
No. of reflections	1941
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.15

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University, the Talent Fund of Ningbo Municipal Natural Science Foundation (grant No. 2010 A610187) and the Talent Fund of Ningbo University (grant No. Xkl09070).

References

Chen, C. L., Goforth, A. M., Smith, M. D., Su, C. Y. & Loye, H. C. (2005). Inorg. Chem. 44, 8762–8769. Web of Science CSD CrossRef PubMed CAS Google Scholar
Harries, H. J. & Orford, B. F. (1983). Inorg. Chim. Acta, 68, 41–43. CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Lindeman, S. V., Shklover, V. E. & Struchkov, Yu. T. (1981). Acta Cryst. A37, C87. CrossRef IUCr Journals Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Rodriguez de Barbarin, C. O., Bailey, N. A., Fenton, D. E. & He, Q. (1994). Inorg. Chim. Acta, 219, 205–207. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xia, D.-G., Ye, Y.-F. & Lei, K.-W. (2009). Acta Cryst. E65, o3168. Web of Science CSD CrossRef IUCr Journals Google Scholar