2-[(E)-(4-Fluoro­benzyl­imino)­meth­yl]-4-methyl­phenol

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

doi:10.1107/S1600536812027018

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2149

https://doi.org/10.1107/S1600536812027018

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2-[(E)-(4-Fluorobenzylimino)methyl]-4-methylphenol

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

^aState Key Lab. 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 21 May 2012; accepted 14 June 2012; online 20 June 2012)

In the title Schiff base compound, C₁₅H₁₄FNO, the benzene rings make a dihedral angle of 72.75 (13)°. The molecular structure is stabilized by an intramolecular O—H⋯N hydrogen bond. In the crystal, weak π–π stacking occurs between the phenol rings of inversion-related molecules, the centroid–centroid distance being 3.7731 (14) Å.

Related literature

For background and related compounds, see: Cohen et al. (1964 ); Xia et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₄FNO
M_r = 243.28
Monoclinic, P 2₁ /c
a = 15.0297 (9) Å
b = 6.1496 (3) Å
c = 14.3090 (9) Å
β = 104.142 (6)°
V = 1282.45 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.38 × 0.21 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
9046 measured reflections
2265 independent reflections
1552 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.150
S = 1.10
2265 reflections
164 parameters
1 restraint
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
O1—H1⋯N1	0.82	1.90	2.628 (3)	147

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/S1600536812027018/xu5548sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S1600536812027018/xu5548Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027018/xu5548Isup3.cml

checkCIF report

Comment top

Schiff base have played an important role in the development of coordination chemistry (Xia et al., 2009) as they readily form stable complexes with most of the transition metals. Some of the reasons are that the N atom plays an important role in the formation of metal complexes, and that Schiff base compounds show photochromism and thermochromism in the solid state by proton transfer from the hydroxyl O atom to the imine N atom (Cohen et al., 1964). Here we report on a new Schiff base.

The molecular structures of(I) illustrated in the Fig. 1. The C8 and N1 atoms form a 1.46 (4) Å single bond is longer than the double bond [1.28 (3) Å] formed by C7 and N1. The molecular structure is stabilized by an intramolecular O—H···N hydrogen bond.

Related literature top

For background and related compounds, see: Cohen et al. (1964); Xia et al. (2009).

Experimental top

2-Hydroxy-4-methylbenzaldehyde (20 mmol, 2.72 g) and (4-fluorophenyl)methanamine (20 mmol, 2.5 g) were dissolved in ethanol respectively. Then put them together and the solution was refluxed for 30 min. Yellow powder precipitates when cooled to room temperature. After evaporation, a crude product was recrystallized twice from methanol to give yellow crystals.

Structure description top

For background and related compounds, see: Cohen et al. (1964); Xia et al. (2009).

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. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.

2-[(E)-(4-Fluorobenzylimino)methyl]-4-methylphenol top

Crystal data top

C₁₅H₁₄FNO	F(000) = 512.0
M_r = 243.28	D_x = 1.260 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2338 reflections
a = 15.0297 (9) Å	θ = 1.0–25.0°
b = 6.1496 (3) Å	µ = 0.09 mm⁻¹
c = 14.3090 (9) Å	T = 293 K
β = 104.142 (6)°	Block, yellow
V = 1282.45 (13) Å³	0.38 × 0.21 × 0.14 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1552 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 25.0°, θ_min = 2.8°
ω scans	h = −17→17
9046 measured reflections	k = −7→7
2265 independent reflections	l = −16→17

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0477P)² + 0.4777P] where P = (F_o² + 2F_c²)/3
2265 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₅H₁₄FNO	V = 1282.45 (13) Å³
M_r = 243.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.0297 (9) Å	µ = 0.09 mm⁻¹
b = 6.1496 (3) Å	T = 293 K
c = 14.3090 (9) Å	0.38 × 0.21 × 0.14 mm
β = 104.142 (6)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1552 reflections with I > 2σ(I)
9046 measured reflections	R_int = 0.030
2265 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	1 restraint
wR(F²) = 0.150	H-atom parameters constrained
S = 1.10	Δρ_max = 0.15 e Å⁻³
2265 reflections	Δρ_min = −0.17 e Å⁻³
164 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
C1	0.02053 (15)	0.5287 (4)	0.65069 (15)	0.0460 (6)
O1	0.10373 (12)	0.2040 (3)	0.63178 (13)	0.0702 (5)
H1	0.1454	0.2793	0.6633	0.105*
C7	0.10205 (17)	0.6427 (4)	0.70213 (16)	0.0553 (6)
H7A	0.0966	0.7852	0.7218	0.066*
C6	0.02389 (17)	0.3154 (4)	0.61582 (16)	0.0515 (6)
C5	−0.05629 (19)	0.2196 (4)	0.56346 (18)	0.0606 (7)
H5A	−0.0550	0.0787	0.5402	0.073*
C3	−0.14383 (18)	0.5419 (4)	0.57872 (17)	0.0587 (7)
C2	−0.06444 (16)	0.6353 (4)	0.63143 (16)	0.0533 (6)
H2A	−0.0671	0.7752	0.6553	0.064*
N1	0.18143 (15)	0.5538 (4)	0.72148 (15)	0.0637 (6)
C4	−0.13757 (18)	0.3317 (5)	0.54576 (17)	0.0624 (7)
H4A	−0.1905	0.2642	0.5103	0.075*
C9	−0.23392 (19)	0.6640 (6)	0.5563 (2)	0.0902 (10)
H9A	−0.2224	0.8168	0.5521	0.135*
H9B	−0.2649	0.6388	0.6066	0.135*
H9C	−0.2717	0.6140	0.4960	0.135*
C10	0.32939 (16)	0.7009 (5)	0.71083 (18)	0.0594 (7)
C8	0.25963 (19)	0.6878 (6)	0.7706 (2)	0.0798 (9)
H8A	0.2878	0.6250	0.8330	0.096*
H8B	0.2385	0.8328	0.7809	0.096*
F1	0.51784 (14)	0.7389 (4)	0.54697 (17)	0.1337 (9)
C15	0.38998 (19)	0.5337 (5)	0.7092 (2)	0.0754 (8)
H15A	0.3883	0.4105	0.7464	0.090*
C13	0.45416 (19)	0.7270 (6)	0.5999 (2)	0.0800 (9)
C11	0.33333 (18)	0.8798 (5)	0.6546 (2)	0.0701 (8)
H11A	0.2928	0.9943	0.6544	0.084*
C14	0.45313 (19)	0.5445 (6)	0.6536 (2)	0.0840 (9)
H14A	0.4937	0.4308	0.6529	0.101*
C12	0.3958 (2)	0.8944 (5)	0.5983 (2)	0.0795 (9)
H12A	0.3976	1.0163	0.5604	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0579 (14)	0.0454 (13)	0.0398 (12)	−0.0019 (11)	0.0216 (10)	0.0035 (10)
O1	0.0752 (12)	0.0557 (11)	0.0887 (13)	0.0113 (9)	0.0373 (10)	−0.0010 (10)
C7	0.0664 (16)	0.0565 (15)	0.0483 (13)	−0.0059 (12)	0.0244 (12)	−0.0014 (12)
C6	0.0675 (16)	0.0451 (14)	0.0507 (13)	0.0023 (12)	0.0312 (12)	0.0029 (11)
C5	0.0812 (18)	0.0508 (15)	0.0591 (15)	−0.0124 (14)	0.0347 (14)	−0.0112 (13)
C3	0.0670 (16)	0.0643 (17)	0.0475 (13)	0.0028 (13)	0.0191 (12)	0.0075 (13)
C2	0.0694 (16)	0.0446 (13)	0.0497 (13)	0.0042 (12)	0.0219 (12)	0.0033 (11)
N1	0.0596 (13)	0.0755 (15)	0.0597 (13)	−0.0104 (12)	0.0216 (11)	−0.0014 (11)
C4	0.0697 (17)	0.0713 (18)	0.0494 (14)	−0.0164 (14)	0.0207 (13)	−0.0049 (14)
C9	0.0684 (19)	0.105 (3)	0.092 (2)	0.0169 (17)	0.0095 (17)	0.018 (2)
C10	0.0463 (14)	0.0720 (18)	0.0561 (15)	−0.0083 (13)	0.0050 (11)	−0.0012 (14)
C8	0.0684 (18)	0.110 (2)	0.0631 (17)	−0.0216 (17)	0.0198 (14)	−0.0138 (17)
F1	0.1096 (15)	0.160 (2)	0.159 (2)	−0.0252 (14)	0.0876 (15)	−0.0185 (16)
C15	0.0673 (18)	0.074 (2)	0.0802 (19)	−0.0018 (15)	0.0096 (15)	0.0124 (16)
C13	0.0612 (18)	0.097 (3)	0.089 (2)	−0.0158 (17)	0.0329 (16)	−0.009 (2)
C11	0.0580 (16)	0.0698 (19)	0.0807 (19)	0.0033 (14)	0.0136 (14)	−0.0013 (16)
C14	0.0587 (17)	0.083 (2)	0.109 (3)	0.0091 (16)	0.0190 (17)	−0.012 (2)
C12	0.078 (2)	0.075 (2)	0.087 (2)	−0.0110 (17)	0.0240 (17)	0.0117 (17)

Geometric parameters (Å, º) top

C1—C2	1.402 (3)	C9—H9B	0.9600
C1—C6	1.409 (3)	C9—H9C	0.9600
C1—C7	1.447 (3)	C10—C11	1.373 (4)
O1—C6	1.352 (3)	C10—C15	1.378 (3)
O1—H1	0.8200	C10—C8	1.508 (3)
C7—N1	1.280 (3)	C8—H8A	0.9700
C7—H7A	0.9300	C8—H8B	0.9700
C6—C5	1.385 (3)	F1—C13	1.360 (3)
C5—C4	1.371 (4)	C15—C14	1.381 (4)
C5—H5A	0.9300	C15—H15A	0.9300
C3—C2	1.372 (3)	C13—C12	1.349 (4)
C3—C4	1.387 (4)	C13—C14	1.362 (4)
C3—C9	1.513 (4)	C11—C12	1.381 (4)
C2—H2A	0.9300	C11—H11A	0.9300
N1—C8	1.466 (3)	C14—H14A	0.9300
C4—H4A	0.9300	C12—H12A	0.9300
C9—H9A	0.9600

C2—C1—C6	118.4 (2)	H9A—C9—H9C	109.5
C2—C1—C7	119.4 (2)	H9B—C9—H9C	109.5
C6—C1—C7	122.2 (2)	C11—C10—C15	117.7 (3)
C6—O1—H1	109.5	C11—C10—C8	120.7 (3)
N1—C7—C1	122.1 (2)	C15—C10—C8	121.6 (3)
N1—C7—H7A	118.9	N1—C8—C10	110.2 (2)
C1—C7—H7A	118.9	N1—C8—H8A	109.6
O1—C6—C5	119.7 (2)	C10—C8—H8A	109.6
O1—C6—C1	121.3 (2)	N1—C8—H8B	109.6
C5—C6—C1	119.1 (2)	C10—C8—H8B	109.6
C4—C5—C6	120.3 (2)	H8A—C8—H8B	108.1
C4—C5—H5A	119.9	C10—C15—C14	121.6 (3)
C6—C5—H5A	119.9	C10—C15—H15A	119.2
C2—C3—C4	117.1 (2)	C14—C15—H15A	119.2
C2—C3—C9	121.4 (3)	C12—C13—F1	119.6 (3)
C4—C3—C9	121.5 (3)	C12—C13—C14	122.7 (3)
C3—C2—C1	122.7 (2)	F1—C13—C14	117.7 (3)
C3—C2—H2A	118.7	C10—C11—C12	121.8 (3)
C1—C2—H2A	118.7	C10—C11—H11A	119.1
C7—N1—C8	117.3 (3)	C12—C11—H11A	119.1
C5—C4—C3	122.5 (2)	C13—C14—C15	118.0 (3)
C5—C4—H4A	118.8	C13—C14—H14A	121.0
C3—C4—H4A	118.8	C15—C14—H14A	121.0
C3—C9—H9A	109.5	C13—C12—C11	118.2 (3)
C3—C9—H9B	109.5	C13—C12—H12A	120.9
H9A—C9—H9B	109.5	C11—C12—H12A	120.9
C3—C9—H9C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.90	2.628 (3)	147

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄FNO
M_r	243.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.0297 (9), 6.1496 (3), 14.3090 (9)
β (°)	104.142 (6)
V (Å³)	1282.45 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.38 × 0.21 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9046, 2265, 1552
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.150, 1.10
No. of reflections	2265
No. of parameters	164
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.17

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), 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
O1—H1···N1	0.82	1.90	2.628 (3)	147

Acknowledgements

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

References

Cohen, M. D., Schmidt, G. M. J. & Flavian, S. (1964). J. Chem. Soc. pp. 2041–2043. CrossRef Web of Science 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
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