4-Fluoro-2-[(3-methyl­phen­yl)imino­meth­yl]phenol

Alice Brink; Hendrik G Visser; Andreas Roodt

doi:10.1107/S1600536812010513

. 2012 Mar 14;68(Pt 4):o1071. doi: 10.1107/S1600536812010513

4-Fluoro-2-[(3-methylphenyl)iminomethyl]phenol

Alice Brink ^a,^*, Hendrik G Visser ^a, Andreas Roodt ^a

PMCID: PMC3344028 PMID: 22589937

Abstract

The title compound, C₁₄H₁₂FNO, crystallizes as the trans phenol–imine tautomer. The two benzene rings are essentially coplanar, being inclined to one another by 9.28 (7)°. This is at least in part due to the intramolecular O—H⋯N hydrogen bond between the hydroxy O atom and the imine N atom. The crystal structure is stabilized by an array of weak C—H⋯O and C—H⋯F interactions, which link the molecules into a stable three-dimensional network.

Related literature

For related structures, see: Karakaş et al. (2004 ▶); Arod et al. (2005 ▶); Cheng et al. (2005 ▶); Brink et al. (2009 ▶). For related rhenium tricarbonyl complexes containing salicylaldimines, see: Brink et al. (2011 ▶). For related N,O-bidentate ligands coordinated to a rhenium tricarbonyl core, see: Schutte et al. (2011 ▶).

Experimental

Crystal data

C₁₄H₁₂FNO
M _r = 229.25
Monoclinic,
a = 10.2655 (6) Å
b = 4.6738 (2) Å
c = 12.3561 (8) Å
β = 112.331 (3)°
V = 548.37 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.19 × 0.1 × 0.06 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.981, T _max = 0.994
7009 measured reflections
1319 independent reflections
1203 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.095
S = 1.06
1319 reflections
156 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ▶); software used to prepare material for publication: WingGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812010513/sj5208sup1.cif

e-68-o1071-sup1.cif^{(16KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010513/sj5208Isup2.hkl

e-68-o1071-Isup2.hkl^{(63.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812010513/sj5208Isup3.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—H1B⋯N1	0.84	1.85	2.601 (2)	147
C1—H1A⋯O1ⁱ	0.95	2.6	3.467 (3)	151
C16—H16⋯O1ⁱ	0.95	2.65	3.495 (3)	149
C13—H13⋯F1ⁱⁱ	0.95	2.6	3.472 (3)	153
C231—H23A⋯F1ⁱⁱⁱ	0.98	2.73	3.321 (3)	119
C231—H23C⋯F1^iv	0.98	2.67	3.193 (2)	114

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

Financial assistance from the University of the Free State (UFS), the UFS Advanced Biomolecular Cluster, SASOL and the South African National Research Foundation (SA-NRF/THRIP) is gratefully acknowledged. Part of this material is based on work supported by the SA-NRF/THRIP under grant No. GUN 2068915. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the SA-NRF.

supplementary crystallographic information

Comment

Schiff-base ligands have played a significant role in the development of coordination chemistry as stable organometallic complexes are readily formed with a variety of transition metals. In continuation of our research on the coordination of various bifunctional chelate systems on the fac-[M(CO)₃]⁺ moiety (M = Re(I), Tc(I)) (Brink et al., 2011; Schutte et al., 2011) the title compound was synthesized and is reported here.

The title compound (Figure 1) is essentially co-planar with a dihedral angle of 9.28 (7)° between the aromatic rings. The bond distances and angles in the title compound are in accord with those reported for related salicylaldimine-based ligand systems (Karakaş et al., 2004; Arod et al., 2005; Cheng et al., 2005; Brink et al., 2009).

The compound crystallizes as the trans phenol-imine tautomer. A strong intramolecular hydrogen bond occurs between the O—H···N atoms in each unique molecule. The crystal structure is stabilized by an array of weak C—H···O and C—H···F interactions. The bifurcated acceptor, O1, experiences weak hydrogen bond interactions with H16 and H1A. As a result, the two independent molecules pack nearly perpendicular to each other with a dihedral angle of 88.01 (5)° between planes drawn through the C1 aromatic ring systems (Figures 2 and 3). All the interactions serve to link the molecules into a stable three-dimensional supramolecular network. The molecular packing, viewed along the c-axis, illustrates the cube-like tunnel formation resulting from the various interactions (Figure 4).

Experimental

The reaction was performed under Schlenk conditions using a nitrogen atmosphere. To a solution of 5-fluorosalicylaldehyde (0.50 g, 3.57 mmol) in methanol, a solution of m-toluidine (0.382 g, 3.57 mmol) was added. The reaction was refluxed at 80°C for 3 h. The solvent was removed under reduced pressure. The product was obtained as an orange solid which was washed with cold methanol and filtered. Crystals suitable for X-ray diffraction were grown from the filtrate. Yield 82.1%. ¹H NMR [acetone-d₆, 600 MHz, δ (p.p.m.)] 13.04 (s, 1H), 8.90 (s, 1H), 7.40 (dd, 1H, J = 3.1, 8.7 Hz), 7.35 (t, 1H, J = 7.7 Hz), 7.25 (s, 1H), 7.24–7.20 (m, 2H), 7.16 (d, 1H, J = 7.7 Hz), 6.96 (dd, 1H, J = 4.5, 9.1 Hz), 2.39 (s, 3H, CH₃).