2-(m-Tolyl­imino­meth­yl)phenol

Brink, A.; Roodt, A.; Visser, H.G.

doi:10.1107/S1600536809049307

organic compounds

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Volume 65| Part 12| December 2009| Pages o3175-o3176

doi:10.1107/S1600536809049307

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2-(m-Tolyliminomethyl)phenol

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

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
^*Correspondence e-mail: alice.brink@gmail.com

(Received 21 October 2009; accepted 18 November 2009; online 21 November 2009)

The title compound, C₁₄H₁₃NO, is non-planar with a dihedral angle of 47.00 (6)° between the planes of the two aromatic rings. Intramolecular hydrogen bonding is observed between the O—H group and the N atom, resulting in a phenol–imine tautomeric form.

Related literature

For related structures, see: Elmali et al. (1998 ); Cheng et al. (2005 ); Arod et al. (2005 ); Bingöl et al. (2007 ); Zhang et al. (2007 ). For macromolecules containing Schiff base–metal complexes see: Leung et al. (2007 ). For related structures with non-linear optical properties, magnetic, oxygen transport and catalytic properties: see Karakas et al. (2004 ); Miyasaka et al. (2003 ); Bailes et al. (1947 ); Zhang et al. (1994 ). For photo-physical properties such as thermochromism and photochromism, see: Gakias et al. (2005 ). For N-Salicylideneaniline, which displays reversible photoreactivity and crystallizes as both non-planar and planar polymorphs, see: Arod et al. (2005, 2007 )

Experimental

Crystal data

C₁₄H₁₃NO
M_r = 211.25
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.4946 (4) Å
b = 11.8669 (6) Å
c = 12.2970 (6) Å
V = 1093.67 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.35 × 0.22 × 0.08 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.972, T_max = 0.994
11186 measured reflections
1532 independent reflections
1210 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.099
S = 1.08
1532 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.84	1.85	2.595 (2)	147

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: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049307/bg2304sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049307/bg2304Isup2.hkl

checkCIF report

Comment top

Schiff bases readily form stable complexes with many transition metals and therefore play an important role in the developement of coordination chemistry. The choice of the appropriate amine and various substituents on the aromatic ring of the carbonyl compound allows for great versatility and fine tuning of the steric and electronic properties. The ligands have interesting photo-physical properties as thermochromism and photochromism (Gakias et al., 2005), such as N-Salicylideneaniline which displays reversible photoreactivity and crystallizes as both non-planar and planar polymorphs (Arod et al., 2005 and 2007).

The title compound (Figure 1) is non-planar with a dihedral angle between aromatic rings of 47.00 (6)°, and a C1—N1—C21—C22 torsion angle of 42.7 (3)° . The C1—N1 bond distance (1.287 (3) Å) confirms to the value for a double bond. The molecule displays a trans configuration with respect to the C1—N1 double bond. The N1—C21 and C1—C11 bond distances are 1.426 (3) and 1.445 (3)Å respectively and all other bond distances are within normal range. The molecule adopts a phenol-imine tautomeric form, with strong intramolecular hydrogen bonding observed (O—H···N = 2.595 (2) Å).

Related literature top

For related structures, see: Elmali et al. (1998); Cheng et al. (2005); Arod et al. (2005); Bingöl et al. (2007); Zhang et al. (2007). For macromolecules containing Schiff base–metal complexes see: Leung et al. (2007). For related structures withg non-linear optical properties, interesting magnetic, oxygen transport and catalytic properties: see Karakas et al. (2004); Miyasaka et al. (2003); Bailes et al. (1947); Zhang et al. (1994). For photo-physical properties as thermochromism and photochromism, see: ; Gakias et al. (2005). For N-Salicylideneaniline, which displays reversible photoreactivity and crystallizes as both non-planar and planar polymorphs, see: Arod et al. (2005, 2007)

Experimental top

Salicylaldehyde (14.0 mmol, 1.71 g) was dissolved in 30 ml methanol. m-Toluidine (14.0 mmol, 1.50 g) dissolved in methanol (10 ml), was added dropwise to the reaction mixture. Anhydrous MgSO₄ was added to the reaction. The mixture was heated to 80° and refluxed for 3 hr. The MgSO₄ was filtered and the yellow product was collected. The solvent was removed under reduced pressure. The product was dissolved in acetone and crystals suitable for x-ray diffraction were obtained by slow evaporation of the solvent at 0°C. Yield 94.4%. ¹H NMR [CDCl₃, 300 MHz, δ(p.p.m.)] 8.6 (1H, s, HCN), 7.4–6.9 (8H, m, Ar), 2.4 (3H, s, CH₃).

Computing details top

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).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

2-(m-Tolyliminomethyl)phenol top

Crystal data top

C₁₄H₁₃NO	F(000) = 448
M_r = 211.25	D_x = 1.283 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1942 reflections
a = 7.4946 (4) Å	θ = 3.2–22.3°
b = 11.8669 (6) Å	µ = 0.08 mm⁻¹
c = 12.2970 (6) Å	T = 100 K
V = 1093.67 (10) Å³	Cuboid, red
Z = 4	0.35 × 0.22 × 0.08 mm

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	1532 independent reflections
Radiation source: sealed tube	1210 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 512 pixels mm^-1	θ_max = 28.0°, θ_min = 2.4°
ω and ϕ scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −15→12
T_min = 0.972, T_max = 0.994	l = −13→16
11186 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0482P)² + 0.0939P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.099	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.20 e Å⁻³
1532 reflections	Δρ_min = −0.21 e Å⁻³
146 parameters

Crystal data top

C₁₄H₁₃NO	V = 1093.67 (10) Å³
M_r = 211.25	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.4946 (4) Å	µ = 0.08 mm⁻¹
b = 11.8669 (6) Å	T = 100 K
c = 12.2970 (6) Å	0.35 × 0.22 × 0.08 mm

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	1532 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1210 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.994	R_int = 0.055
11186 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.08	Δρ_max = 0.20 e Å⁻³
1532 reflections	Δρ_min = −0.21 e Å⁻³
146 parameters

Special details top

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 60 s/frame. A total of 1032 frames were collected with a frame width of 0.5° covering up to θ = 27.99° with 100.0% completeness accomplized.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.4954 (3)	0.32440 (17)	0.70887 (17)	0.0219 (5)
H1	0.4568	0.2514	0.6877	0.026*
C231	0.5244 (3)	0.15389 (17)	0.30941 (18)	0.0272 (5)
H2A	0.584	0.1037	0.3612	0.041*
H2B	0.6073	0.1733	0.2507	0.041*
H2C	0.4198	0.1158	0.2789	0.041*
C11	0.5390 (3)	0.34554 (16)	0.82153 (17)	0.0209 (5)
C12	0.6066 (3)	0.45064 (17)	0.85663 (18)	0.0223 (5)
C13	0.6401 (3)	0.46927 (19)	0.96612 (18)	0.0257 (5)
H13	0.6882	0.5393	0.9893	0.031*
C14	0.6037 (3)	0.38626 (18)	1.0414 (2)	0.0281 (5)
H14	0.6248	0.4004	1.1163	0.034*
C15	0.5364 (3)	0.28196 (18)	1.00924 (18)	0.0290 (6)
H15	0.5114	0.2252	1.0616	0.035*
C16	0.5066 (3)	0.26242 (17)	0.90006 (17)	0.0242 (5)
H16	0.4631	0.1909	0.8776	0.029*
C21	0.4611 (3)	0.37863 (16)	0.52673 (17)	0.0207 (5)
C22	0.5118 (3)	0.27911 (17)	0.47524 (17)	0.0214 (5)
H22	0.5779	0.224	0.5142	0.026*
C23	0.4662 (3)	0.25991 (17)	0.36708 (18)	0.0214 (5)
C24	0.3690 (3)	0.34139 (17)	0.31147 (18)	0.0237 (5)
H24	0.3362	0.329	0.2378	0.028*
C25	0.3195 (3)	0.44076 (17)	0.36278 (19)	0.0258 (5)
H25	0.2525	0.4956	0.3241	0.031*
C26	0.3668 (3)	0.46058 (17)	0.46985 (18)	0.0240 (5)
H26	0.3351	0.5295	0.5042	0.029*
N1	0.5078 (2)	0.40260 (13)	0.63674 (14)	0.0213 (4)
O1	0.6371 (2)	0.53517 (12)	0.78487 (12)	0.0274 (4)
H1A	0.6018	0.5156	0.7228	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0191 (12)	0.0190 (10)	0.0276 (12)	0.0004 (9)	0.0021 (11)	−0.0022 (9)
C231	0.0276 (13)	0.0287 (11)	0.0253 (11)	0.0035 (10)	−0.0034 (11)	−0.0028 (10)
C11	0.0200 (11)	0.0176 (10)	0.0251 (11)	0.0030 (9)	0.0013 (10)	−0.0020 (9)
C12	0.0176 (11)	0.0205 (11)	0.0287 (13)	0.0023 (9)	0.0018 (10)	−0.0013 (10)
C13	0.0202 (12)	0.0232 (10)	0.0338 (13)	−0.0003 (10)	−0.0021 (11)	−0.0064 (10)
C14	0.0272 (13)	0.0303 (12)	0.0267 (12)	0.0029 (11)	−0.0032 (11)	−0.0054 (10)
C15	0.0341 (14)	0.0269 (12)	0.0260 (12)	0.0025 (11)	0.0013 (11)	0.0023 (10)
C16	0.0276 (13)	0.0208 (10)	0.0242 (12)	0.0002 (10)	0.0021 (10)	−0.0015 (8)
C21	0.0174 (11)	0.0218 (10)	0.0227 (12)	−0.0051 (9)	0.0036 (10)	0.0035 (9)
C22	0.0191 (11)	0.0213 (10)	0.0238 (12)	0.0013 (9)	0.0002 (10)	0.0031 (9)
C23	0.0161 (11)	0.0235 (10)	0.0247 (11)	−0.0032 (9)	0.0010 (10)	0.0018 (9)
C24	0.0182 (11)	0.0325 (12)	0.0203 (11)	−0.0023 (10)	0.0003 (10)	0.0060 (10)
C25	0.0222 (12)	0.0245 (12)	0.0305 (13)	0.0001 (9)	0.0006 (11)	0.0100 (10)
C26	0.0202 (12)	0.0187 (10)	0.0331 (13)	0.0002 (10)	0.0029 (11)	0.0032 (10)
N1	0.0208 (10)	0.0213 (9)	0.0219 (9)	0.0016 (8)	0.0019 (9)	0.0001 (7)
O1	0.0315 (9)	0.0207 (7)	0.0300 (8)	−0.0036 (7)	−0.0004 (8)	−0.0007 (7)

Geometric parameters (Å, º) top

C1—N1	1.287 (3)	C15—C16	1.381 (3)
C1—C11	1.445 (3)	C15—H15	0.95
C1—H1	0.95	C16—H16	0.95
C231—C23	1.509 (3)	C21—C26	1.391 (3)
C231—H2A	0.98	C21—C22	1.393 (3)
C231—H2B	0.98	C21—N1	1.426 (3)
C231—H2C	0.98	C22—C23	1.392 (3)
C11—C16	1.402 (3)	C22—H22	0.95
C11—C12	1.414 (3)	C23—C24	1.390 (3)
C12—O1	1.355 (2)	C24—C25	1.388 (3)
C12—C13	1.387 (3)	C24—H24	0.95
C13—C14	1.379 (3)	C25—C26	1.384 (3)
C13—H13	0.95	C25—H25	0.95
C14—C15	1.394 (3)	C26—H26	0.95
C14—H14	0.95	O1—H1A	0.84

N1—C1—C11	121.27 (18)	C15—C16—C11	121.6 (2)
N1—C1—H1	119.4	C15—C16—H16	119.2
C11—C1—H1	119.4	C11—C16—H16	119.2
C23—C231—H2A	109.5	C26—C21—C22	120.19 (19)
C23—C231—H2B	109.5	C26—C21—N1	117.55 (18)
H2A—C231—H2B	109.5	C22—C21—N1	122.22 (18)
C23—C231—H2C	109.5	C23—C22—C21	120.40 (19)
H2A—C231—H2C	109.5	C23—C22—H22	119.8
H2B—C231—H2C	109.5	C21—C22—H22	119.8
C16—C11—C12	118.21 (19)	C24—C23—C22	119.0 (2)
C16—C11—C1	119.93 (18)	C24—C23—C231	120.03 (19)
C12—C11—C1	121.80 (18)	C22—C23—C231	121.0 (2)
O1—C12—C13	118.91 (19)	C25—C24—C23	120.5 (2)
O1—C12—C11	120.96 (19)	C25—C24—H24	119.8
C13—C12—C11	120.1 (2)	C23—C24—H24	119.8
C14—C13—C12	120.1 (2)	C26—C25—C24	120.6 (2)
C14—C13—H13	119.9	C26—C25—H25	119.7
C12—C13—H13	119.9	C24—C25—H25	119.7
C13—C14—C15	121.0 (2)	C25—C26—C21	119.3 (2)
C13—C14—H14	119.5	C25—C26—H26	120.3
C15—C14—H14	119.5	C21—C26—H26	120.3
C16—C15—C14	118.9 (2)	C1—N1—C21	119.49 (16)
C16—C15—H15	120.5	C12—O1—H1A	109.5
C14—C15—H15	120.5

N1—C1—C11—C16	173.3 (2)	C26—C21—C22—C23	−1.1 (3)
N1—C1—C11—C12	−3.6 (3)	N1—C21—C22—C23	−178.81 (19)
C16—C11—C12—O1	−178.59 (19)	C21—C22—C23—C24	−0.2 (3)
C1—C11—C12—O1	−1.6 (3)	C21—C22—C23—C231	178.35 (19)
C16—C11—C12—C13	0.4 (3)	C22—C23—C24—C25	0.5 (3)
C1—C11—C12—C13	177.4 (2)	C231—C23—C24—C25	−178.0 (2)
O1—C12—C13—C14	177.47 (19)	C23—C24—C25—C26	0.3 (3)
C11—C12—C13—C14	−1.5 (3)	C24—C25—C26—C21	−1.5 (3)
C12—C13—C14—C15	1.3 (3)	C22—C21—C26—C25	1.9 (3)
C13—C14—C15—C16	0.1 (4)	N1—C21—C26—C25	179.75 (19)
C14—C15—C16—C11	−1.3 (4)	C11—C1—N1—C21	−179.12 (19)
C12—C11—C16—C15	1.0 (3)	C26—C21—N1—C1	139.4 (2)
C1—C11—C16—C15	−176.0 (2)	C22—C21—N1—C1	−42.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84	1.85	2.595 (2)	147

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃NO
M_r	211.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.4946 (4), 11.8669 (6), 12.2970 (6)
V (Å³)	1093.67 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.22 × 0.08

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.972, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	11186, 1532, 1210
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.099, 1.08
No. of reflections	1532
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2004), WingGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84	1.85	2.595 (2)	147.2

Acknowledgements

Financial assistance from the University of the Free State is gratefully acknowledged. Mr Leo Kirsten is thanked for the data collection. Gratitude is expressed to SASOL and the South African National Research Foundation (SA-NRF/THRIP) for financial support of this project. 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.

References

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Volume 65| Part 12| December 2009| Pages o3175-o3176

doi:10.1107/S1600536809049307

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