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

Abstract

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,

• a = 15.0297 (9) Å

• b = 6.1496 (3) Å

• c = 14.3090 (9) Å

• β = 104.142 (6)°

• V = 1282.45 (13) ų

• 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[F ² > 2σ(F ²)] = 0.060

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812027018/xu5548Isup3.cml

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

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93– 0.97, O—H = 0.82 Å). U_iso(H) = 1.5U_eq(O) and 1.2U_eq(C).

Figures

Fig. 1.

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

Crystal data

C15H14FNO	F(000) = 512.0
Mr = 243.28	Dx = 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

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

Refinement

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(Fo2) + (0.0477P)2 + 0.4777P] where P = (Fo2 + 2Fc2)/3
2265 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.15 e Å−3
1 restraint	Δρmin = −0.17 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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