(E)-2-Methyl-6-{[(5-methyl­pyridin-2-yl)imino]­methyl}phenol

Arafath, M.A.; Adam, F.; Razali, M.R.

doi:10.1107/S2414314616020095

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x162009

https://doi.org/10.1107/S2414314616020095

Open

access

(E)-2-Methyl-6-{[(5-methylpyridin-2-yl)imino]methyl}phenol

Md. Azharul Arafath,^a Farook Adam ^a ^* and Mohd. R. Razali ^a

^aThe School of Chemical Sciences, Universiti Sains Malaysia (USM), Penang, 11800, Malaysia
^*Correspondence e-mail: farookdr@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 17 December 2016; accepted 17 December 2016; online 6 January 2017)

In the title compound, C₁₄H₁₄N₂O, the dihedral angle between the aromatic rings is 5.54 (9)°. The conformation is reinforced by an intramolecular O—H⋯N hydrogen bond, which closes an S(6) ring. The pyridine N atom and methyl group lie to opposite sides of the molecule. In the crystal, the molecules are linked into a zigzag chain propagating in [0-11] by weak C—H⋯O hydrogen bonds.

Keywords: crystal structure; heterocyclic Schiff base; planar molecule; hydrogen bonding.

CCDC reference: 1513723

Structure description

As part of our ongoing studies of phenolic Schiff-base compounds (Adam et al. (2015 ), we now describe the synthesis and structure of the title compound (Fig. 1), which features an intramolecular O—H⋯N hydrogen bond (Table 1), which helps to establish near-coplanarity of the aromatic rings [dihedral angle = 5.54 (9)°]. In the crystal, the molecules are linked by a C2—H2A—O1 hydrogen bond into a zigzag C(9) chain propagating in [0 $[\overline{1}]$ 1] (Table 1, Fig. 2). Adjacent molecules in the chain are related by c-glide symmetry.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H101⋯N2	0.87 (3)	1.82 (3)	2.590 (2)	146 (3)
C2—H2A⋯O1ⁱ	0.95	2.52	3.322 (3)	142
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+1, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids.

Figure 2
The packing of the title compound viewed along [010].

Synthesis and crystallization

The synthesis scheme is shown in Fig. 3. 2-Hydroxy-3-methylbenzaldehyde (0.681 g, 5 mmol) was dissolved in 20 ml toluene and after adding 0.2 ml acetic acid, the mixture was refluxed for 30 min. Then, 5-methylpyridin-2-amine 0.541 g (5 mmol) solution in 20 ml toluene was added dropwise with stirring to the aldehyde solution. The resulting light-yellow solution was refluxed for 4 h with stirring. The solvent was allowed to evaporate. The crude product was washed with benzene and n-hexane. Orange blocks were obtained by slow evaporation of a solution in toluene; m.p.: 363–364 K; yield: 95%.

Figure 3
Synthesis of the title compound

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₂O
M_r	226.27
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	23.440 (3), 4.6307 (6), 10.6408 (13)
V (Å³)	1155.0 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.59 × 0.18 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9247, 3106, 2792
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.09
No. of reflections	3106
No. of parameters	160
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.18
Computer programs: APEX2 and SAINT (Bruker, 2004 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1513723

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020095/hb4107sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020095/hb4107Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616020095/hb4107Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

(E)-2-Methyl-6-{[(5-methylpyridin-2-yl)imino]methyl}phenol top

Crystal data top

C₁₄H₁₄N₂O	D_x = 1.301 Mg m⁻³
M_r = 226.27	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 2856 reflections
a = 23.440 (3) Å	θ = 2.6–29.1°
b = 4.6307 (6) Å	µ = 0.08 mm⁻¹
c = 10.6408 (13) Å	T = 100 K
V = 1155.0 (3) Å³	Block, orange
Z = 4	0.59 × 0.18 × 0.14 mm
F(000) = 480

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.031
φ and ω scans	θ_max = 29.1°, θ_min = 1.7°
9247 measured reflections	h = −31→31
3106 independent reflections	k = −6→6
2792 reflections with I > 2σ(I)	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0653P)² + 0.0393P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3106 reflections	Δρ_max = 0.25 e Å⁻³
160 parameters	Δρ_min = −0.18 e Å⁻³
1 restraint

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O1	0.65226 (6)	0.0538 (3)	0.69407 (15)	0.0236 (4)
N1	0.61387 (7)	0.6480 (3)	0.31428 (17)	0.0194 (4)
N2	0.63432 (7)	0.3591 (4)	0.49405 (16)	0.0177 (4)
C1	0.70576 (8)	0.6813 (4)	0.4124 (2)	0.0204 (4)
H1A	0.7307	0.6230	0.4781	0.025*
C2	0.72340 (9)	0.8817 (4)	0.3237 (2)	0.0212 (4)
H2A	0.7608	0.9600	0.3273	0.025*
C3	0.68583 (8)	0.9677 (4)	0.22889 (19)	0.0185 (4)
C4	0.63168 (9)	0.8438 (4)	0.2302 (2)	0.0197 (4)
H4A	0.6055	0.9022	0.1669	0.024*
C5	0.65087 (8)	0.5669 (4)	0.40364 (19)	0.0170 (4)
C6	0.70294 (9)	1.1822 (4)	0.1299 (2)	0.0228 (4)
H6A	0.6696	1.2327	0.0788	0.034*
H6B	0.7324	1.0974	0.0760	0.034*
H6C	0.7180	1.3566	0.1702	0.034*
C7	0.58560 (9)	0.2307 (4)	0.48190 (19)	0.0178 (4)
H7A	0.5619	0.2782	0.4125	0.021*
C8	0.56627 (8)	0.0167 (4)	0.57120 (18)	0.0168 (4)
C9	0.51292 (9)	−0.1140 (4)	0.5548 (2)	0.0205 (4)
H9A	0.4899	−0.0613	0.4849	0.025*
C10	0.49335 (9)	−0.3183 (4)	0.6386 (2)	0.0232 (4)
H10A	0.4570	−0.4051	0.6272	0.028*
C11	0.52755 (9)	−0.3965 (4)	0.7406 (2)	0.0222 (4)
H11A	0.5139	−0.5377	0.7981	0.027*
C12	0.58079 (9)	−0.2740 (4)	0.76055 (19)	0.0205 (4)
C13	0.60016 (8)	−0.0652 (4)	0.67508 (19)	0.0181 (4)
C14	0.61778 (10)	−0.3582 (5)	0.8700 (2)	0.0290 (5)
H14A	0.6269	−0.1862	0.9198	0.043*
H14B	0.6532	−0.4453	0.8388	0.043*
H14C	0.5974	−0.4980	0.9226	0.043*
H101	0.6583 (13)	0.190 (7)	0.639 (3)	0.046 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0218 (7)	0.0269 (8)	0.0221 (8)	−0.0048 (6)	−0.0036 (6)	0.0055 (7)
N1	0.0210 (8)	0.0201 (8)	0.0170 (8)	0.0000 (7)	−0.0007 (7)	0.0006 (7)
N2	0.0182 (8)	0.0172 (8)	0.0178 (8)	0.0001 (6)	0.0024 (6)	0.0005 (7)
C1	0.0190 (10)	0.0206 (9)	0.0217 (11)	−0.0005 (7)	−0.0031 (8)	0.0039 (8)
C2	0.0204 (9)	0.0210 (9)	0.0222 (10)	−0.0015 (8)	0.0014 (8)	0.0014 (9)
C3	0.0233 (10)	0.0163 (9)	0.0159 (9)	0.0013 (7)	0.0029 (7)	−0.0011 (8)
C4	0.0234 (10)	0.0186 (9)	0.0170 (9)	0.0021 (7)	−0.0009 (8)	0.0006 (8)
C5	0.0211 (9)	0.0148 (9)	0.0150 (9)	0.0005 (7)	0.0013 (7)	−0.0003 (7)
C6	0.0288 (11)	0.0200 (10)	0.0196 (10)	0.0007 (8)	0.0037 (8)	0.0039 (8)
C7	0.0197 (9)	0.0168 (8)	0.0169 (10)	0.0018 (7)	0.0016 (7)	−0.0009 (8)
C8	0.0184 (9)	0.0165 (8)	0.0156 (10)	0.0020 (7)	0.0023 (7)	−0.0006 (7)
C9	0.0199 (10)	0.0195 (9)	0.0222 (10)	0.0016 (7)	0.0009 (8)	−0.0015 (8)
C10	0.0190 (9)	0.0224 (10)	0.0281 (11)	−0.0001 (8)	0.0034 (8)	−0.0007 (9)
C11	0.0268 (10)	0.0183 (9)	0.0217 (11)	0.0008 (8)	0.0081 (8)	0.0008 (8)
C12	0.0248 (10)	0.0209 (10)	0.0158 (10)	0.0022 (8)	0.0030 (8)	0.0014 (8)
C13	0.0195 (9)	0.0183 (8)	0.0164 (10)	0.0012 (7)	0.0014 (7)	−0.0025 (8)
C14	0.0349 (12)	0.0318 (12)	0.0202 (11)	−0.0005 (9)	−0.0005 (9)	0.0069 (10)

Geometric parameters (Å, º) top

O1—C13	1.355 (2)	C6—H6C	0.9800
O1—H101	0.87 (4)	C7—C8	1.446 (3)
N1—C4	1.341 (3)	C7—H7A	0.9500
N1—C5	1.341 (3)	C8—C9	1.401 (3)
N2—C7	1.294 (3)	C8—C13	1.413 (3)
N2—C5	1.415 (2)	C9—C10	1.379 (3)
C1—C2	1.387 (3)	C9—H9A	0.9500
C1—C5	1.395 (3)	C10—C11	1.397 (3)
C1—H1A	0.9500	C10—H10A	0.9500
C2—C3	1.397 (3)	C11—C12	1.387 (3)
C2—H2A	0.9500	C11—H11A	0.9500
C3—C4	1.393 (3)	C12—C13	1.403 (3)
C3—C6	1.503 (3)	C12—C14	1.503 (3)
C4—H4A	0.9500	C14—H14A	0.9800
C6—H6A	0.9800	C14—H14B	0.9800
C6—H6B	0.9800	C14—H14C	0.9800

C13—O1—H101	110 (2)	C8—C7—H7A	119.1
C4—N1—C5	117.50 (17)	C9—C8—C13	118.92 (17)
C7—N2—C5	119.12 (17)	C9—C8—C7	119.61 (18)
C2—C1—C5	118.93 (19)	C13—C8—C7	121.47 (17)
C2—C1—H1A	120.5	C10—C9—C8	120.8 (2)
C5—C1—H1A	120.5	C10—C9—H9A	119.6
C1—C2—C3	119.62 (18)	C8—C9—H9A	119.6
C1—C2—H2A	120.2	C9—C10—C11	119.32 (19)
C3—C2—H2A	120.2	C9—C10—H10A	120.3
C4—C3—C2	116.74 (18)	C11—C10—H10A	120.3
C4—C3—C6	121.49 (18)	C12—C11—C10	121.93 (19)
C2—C3—C6	121.77 (18)	C12—C11—H11A	119.0
N1—C4—C3	124.66 (19)	C10—C11—H11A	119.0
N1—C4—H4A	117.7	C11—C12—C13	118.30 (19)
C3—C4—H4A	117.7	C11—C12—C14	122.09 (19)
N1—C5—C1	122.52 (18)	C13—C12—C14	119.61 (19)
N1—C5—N2	119.71 (17)	O1—C13—C12	118.38 (18)
C1—C5—N2	117.77 (18)	O1—C13—C8	120.94 (17)
C3—C6—H6A	109.5	C12—C13—C8	120.67 (17)
C3—C6—H6B	109.5	C12—C14—H14A	109.5
H6A—C6—H6B	109.5	C12—C14—H14B	109.5
C3—C6—H6C	109.5	H14A—C14—H14B	109.5
H6A—C6—H6C	109.5	C12—C14—H14C	109.5
H6B—C6—H6C	109.5	H14A—C14—H14C	109.5
N2—C7—C8	121.73 (18)	H14B—C14—H14C	109.5
N2—C7—H7A	119.1

C5—C1—C2—C3	0.9 (3)	C13—C8—C9—C10	0.4 (3)
C1—C2—C3—C4	0.2 (3)	C7—C8—C9—C10	−179.86 (18)
C1—C2—C3—C6	−179.50 (18)	C8—C9—C10—C11	−0.5 (3)
C5—N1—C4—C3	0.2 (3)	C9—C10—C11—C12	0.2 (3)
C2—C3—C4—N1	−0.8 (3)	C10—C11—C12—C13	0.2 (3)
C6—C3—C4—N1	178.89 (19)	C10—C11—C12—C14	−179.8 (2)
C4—N1—C5—C1	1.0 (3)	C11—C12—C13—O1	−179.71 (18)
C4—N1—C5—N2	−179.48 (17)	C14—C12—C13—O1	0.3 (3)
C2—C1—C5—N1	−1.6 (3)	C11—C12—C13—C8	−0.3 (3)
C2—C1—C5—N2	178.90 (18)	C14—C12—C13—C8	179.73 (18)
C7—N2—C5—N1	6.5 (3)	C9—C8—C13—O1	179.42 (17)
C7—N2—C5—C1	−174.01 (18)	C7—C8—C13—O1	−0.3 (3)
C5—N2—C7—C8	−179.94 (17)	C9—C8—C13—C12	0.0 (3)
N2—C7—C8—C9	179.30 (18)	C7—C8—C13—C12	−179.77 (18)
N2—C7—C8—C13	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H101···N2	0.87 (3)	1.82 (3)	2.590 (2)	146 (3)
C2—H2A···O1ⁱ	0.95	2.52	3.322 (3)	142

Symmetry code: (i) −x+3/2, y+1, z−1/2.

Acknowledgements

The research was supported financially by the RU grant 1001/PKIMIA/811269 from University Sains Malaysia. The authors wish to thank Universiti Sains Malaysia and The World Academy of Science for (TWAS-USM) fellowship to Md. Azharul Arafath. Md. Azharul Arafath also wishes to acknowledge Shahjalal University of Science and Technology, Sylhet, Bangladesh for study leave.

Funding information

Funding for this research was provided by: University Sains Malaysia (award No. RU grant 1001/PKIMIA/811269); The World Academy of Science

References

Adam, F., Arafath, M. A., Rosenani, A. H. & Razali, M. R. (2015). Acta Cryst. E71, o971–o972. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar