2-Meth­oxy-6-[(Z)-[(5-methyl-2-pyrid­yl)imino­meth­yl]phenol

Liu, X.-Y.; Fan, Y.-H.; Bi, C.-F.; Wang, Q.; Gao, Y.

doi:10.1107/S1600536809031699

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2170

doi:10.1107/S1600536809031699

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2-Methoxy-6-[(Z)-[(5-methyl-2-pyridyl)iminomethyl]phenol

Xin-Yu Liu,^a Yu-Hua Fan,^a ^* Cai-Feng Bi,^a Qiang Wang ^a and Yuan Gao ^a

^aKey Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100, People's Republic of China
^*Correspondence e-mail: fanyuhua301@163.com

(Received 29 July 2009; accepted 11 August 2009; online 15 August 2009)

The title compound, C₁₄H₁₄N₂O₂, was obtained by a condensation reaction between o-vanillin and 5-methylpyridin-2-amine. In the molecule, the dihedral angle between the pyridine and benzene rings is 9.08 (13)°. An intramolecular hydrogen bond involving the imine N atom and the hydroxyl group may influence the conformation of the molecule. The crystal structure is stabilized by weak C—H⋯O hydrogen bonds.

Related literature

For general background to the use of Schiff bases as ligands in coordination chemistry, see: Yamada, (1999 ). For their biological activity, see: Yang et al. (2000 ). For a related structure, see: Dal et al. (2007 ).

Experimental

Crystal data

C₁₄H₁₄N₂O₂
M_r = 242.27
Monoclinic, P 2₁ /c
a = 11.5995 (6) Å
b = 4.9546 (2) Å
c = 23.9983 (12) Å
β = 117.6090 (4)°
V = 1222.15 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.42 × 0.10 × 0.10 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.963, T_max = 0.991
13275 measured reflections
2806 independent reflections
1822 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.198
S = 1.03
2806 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N2	0.82	1.84	2.5587 (19)	146
C3—H3⋯O2ⁱ	0.93	2.64	3.567 (3)	175
C4—H4⋯O1ⁱ	0.93	2.66	3.282 (2)	125
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031699/lh2873sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031699/lh2873Isup2.hkl

checkCIF report

Comment top

Schiff bases are used extensively as ligands in the field of coordination chemistry (Yamada, 1999), and thay have diverse biological activities, such as antibacterial and antitumor activities (Yang et al., 2000). An example of the crystal structure of one such compound, 2-[(1E)-2-aza-2-(5-methyl(2-pyridyl)ethenyl)]-4-bromobenzen-1-ol, is available in the literature (Dal et al., 2007). Herein, the crystal structure of the title compound is presented.

The molecular structure of the title compound is shown in Fig. 1. The molecule contains two aromatic rings linked through a imine group. the dihedral angle between the pyridine and the benzene ring is 9.08 (13)°. An intramolecular O—H···N hydrogen bond in the molecular structure is similar to that in the reported structure (Dal et al., 2007). The crystal structure is stabilized by very weak C-H···O hydrogen bonds (Fig. 2).

Related literature top

For general background to the use of Schiff bases as ligands in coordination chemistry, see: Yamada, (1999). For their biological activity, see: Yang et al. (2000). For a related structure, see: Dal et al. (2007).

Experimental top

All chemicals were analytical reagent grade and used directly without further purification. O-vanillin (1 mmol, 152.1 mg) was added with stirring to anhydrous ethanol (30 ml) and the mixture was slowly dropped into an anhydrous ethanol solution (15 ml) containing (1 mmol, 108.1 mg) 5-methylpyridin-2-amine at 339 K and was then stirred for 4 h, a red solid then separated out. The product was collected by filtration and washed several times with anhydrous ethanol and dried under vacuum. Red single crystals suitable for X-ray diffraction were obtained after 4 days by slow evaporation at room temperature of an anhydrous ethanol solution of the title compound.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. The dashed line indicates a hydrogen bond.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

2-Methoxy-6-[(Z)-[(5-methyl-2-pyridyl)iminomethyl]phenol top

Crystal data top

C₁₄H₁₄N₂O₂	F(000) = 512
M_r = 242.27	D_x = 1.317 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2267 reflections
a = 11.5995 (6) Å	θ = 3.3–24.6°
b = 4.9546 (2) Å	µ = 0.09 mm⁻¹
c = 23.9983 (12) Å	T = 296 K
β = 117.6090°	Neddle, red
V = 1222.15 (10) Å³	0.42 × 0.10 × 0.10 mm
Z = 4

Data collection top

Siemens SMART CCD area-detector diffractometer	2806 independent reflections
Radiation source: fine-focus sealed tube	1822 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→15
T_min = 0.963, T_max = 0.991	k = −6→6
13275 measured reflections	l = −31→30

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.198	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1232P)² + 0.0489P] where P = (F_o² + 2F_c²)/3
2806 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₄N₂O₂	V = 1222.15 (10) Å³
M_r = 242.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5995 (6) Å	µ = 0.09 mm⁻¹
b = 4.9546 (2) Å	T = 296 K
c = 23.9983 (12) Å	0.42 × 0.10 × 0.10 mm
β = 117.6090°

Data collection top

Siemens SMART CCD area-detector diffractometer	2806 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1822 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.991	R_int = 0.049
13275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.198	H-atom parameters constrained
S = 1.03	Δρ_max = 0.25 e Å⁻³
2806 reflections	Δρ_min = −0.22 e Å⁻³
166 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	1.3545 (2)	1.1391 (4)	0.42144 (10)	0.0552 (6)
H1A	1.4361	1.0529	0.4317	0.083*
H1B	1.3646	1.2560	0.4553	0.083*
H1C	1.3275	1.2431	0.3837	0.083*
C2	1.25384 (18)	0.9287 (4)	0.41151 (9)	0.0435 (5)
C3	1.2184 (2)	0.8629 (4)	0.45776 (9)	0.0518 (5)
H3	1.2577	0.9487	0.4966	0.062*
C4	1.1247 (2)	0.6699 (4)	0.44540 (10)	0.0521 (5)
H4	1.1000	0.6241	0.4759	0.063*
C5	1.06743 (18)	0.5443 (4)	0.38751 (9)	0.0418 (5)
C6	1.18963 (19)	0.7932 (4)	0.35514 (9)	0.0470 (5)
H6	1.2118	0.8371	0.3236	0.056*
C7	0.92176 (17)	0.2020 (4)	0.32757 (8)	0.0411 (5)
H7	0.9509	0.2221	0.2976	0.049*
C8	0.82147 (17)	0.0051 (4)	0.31741 (8)	0.0388 (4)
C9	0.77601 (18)	−0.0253 (4)	0.36199 (9)	0.0420 (5)
C10	0.67807 (19)	−0.2169 (4)	0.35134 (9)	0.0454 (5)
C11	0.62864 (19)	−0.3719 (4)	0.29787 (9)	0.0473 (5)
H11	0.5642	−0.4986	0.2910	0.057*
C12	0.6744 (2)	−0.3404 (4)	0.25398 (9)	0.0477 (5)
H12	0.6396	−0.4453	0.2177	0.057*
C13	0.76972 (19)	−0.1575 (4)	0.26345 (9)	0.0444 (5)
H13	0.8004	−0.1407	0.2340	0.053*
C14	0.5556 (2)	−0.4409 (5)	0.39416 (11)	0.0647 (7)
H14A	0.4731	−0.4166	0.3576	0.097*
H14B	0.5437	−0.4396	0.4312	0.097*
H14C	0.5926	−0.6105	0.3913	0.097*
N1	1.09794 (16)	0.6034 (3)	0.34181 (7)	0.0468 (4)
N2	0.97078 (15)	0.3485 (3)	0.37709 (7)	0.0439 (4)
O1	0.82133 (16)	0.1211 (3)	0.41479 (7)	0.0617 (5)
H1	0.8722	0.2352	0.4145	0.093*
O2	0.64070 (16)	−0.2284 (3)	0.39775 (7)	0.0662 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0492 (12)	0.0508 (13)	0.0651 (13)	−0.0111 (10)	0.0261 (10)	0.0039 (10)
C2	0.0383 (10)	0.0425 (11)	0.0525 (11)	−0.0024 (8)	0.0235 (8)	0.0047 (8)
C3	0.0529 (12)	0.0577 (13)	0.0463 (11)	−0.0142 (10)	0.0241 (9)	−0.0060 (9)
C4	0.0572 (13)	0.0622 (13)	0.0474 (11)	−0.0159 (10)	0.0330 (10)	−0.0029 (9)
C5	0.0396 (10)	0.0420 (11)	0.0496 (10)	−0.0038 (8)	0.0255 (9)	0.0022 (8)
C6	0.0483 (11)	0.0510 (12)	0.0521 (11)	−0.0084 (9)	0.0320 (9)	0.0024 (9)
C7	0.0359 (9)	0.0466 (11)	0.0447 (10)	0.0008 (8)	0.0220 (8)	0.0051 (8)
C8	0.0368 (10)	0.0375 (10)	0.0445 (10)	0.0010 (7)	0.0209 (8)	0.0034 (7)
C9	0.0426 (10)	0.0428 (11)	0.0457 (10)	−0.0078 (8)	0.0248 (8)	−0.0038 (8)
C10	0.0443 (10)	0.0465 (11)	0.0553 (11)	−0.0076 (8)	0.0314 (9)	−0.0038 (8)
C11	0.0422 (10)	0.0428 (11)	0.0562 (11)	−0.0065 (8)	0.0222 (9)	−0.0024 (8)
C12	0.0497 (11)	0.0462 (11)	0.0452 (10)	−0.0023 (9)	0.0203 (9)	−0.0047 (8)
C13	0.0465 (11)	0.0476 (12)	0.0445 (10)	−0.0003 (8)	0.0255 (9)	0.0004 (8)
C14	0.0669 (15)	0.0673 (15)	0.0784 (16)	−0.0255 (12)	0.0493 (13)	−0.0062 (12)
N1	0.0469 (9)	0.0522 (10)	0.0478 (9)	−0.0090 (8)	0.0274 (8)	−0.0010 (7)
N2	0.0397 (9)	0.0464 (10)	0.0512 (9)	−0.0083 (7)	0.0257 (7)	0.0000 (7)
O1	0.0707 (10)	0.0734 (11)	0.0594 (9)	−0.0352 (8)	0.0457 (8)	−0.0245 (8)
O2	0.0782 (11)	0.0697 (11)	0.0738 (10)	−0.0374 (9)	0.0548 (9)	−0.0209 (8)

Geometric parameters (Å, º) top

C1—C2	1.500 (3)	C8—C13	1.402 (3)
C1—H1A	0.9600	C8—C9	1.403 (2)
C1—H1B	0.9600	C9—O1	1.338 (2)
C1—H1C	0.9600	C9—C10	1.410 (3)
C2—C6	1.379 (3)	C10—O2	1.371 (2)
C2—C3	1.389 (3)	C10—C11	1.372 (3)
C3—C4	1.373 (3)	C11—C12	1.391 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.380 (3)	C12—C13	1.365 (3)
C4—H4	0.9300	C12—H12	0.9300
C5—N1	1.332 (2)	C13—H13	0.9300
C5—N2	1.414 (2)	C14—O2	1.418 (2)
C6—N1	1.342 (2)	C14—H14A	0.9600
C6—H6	0.9300	C14—H14B	0.9600
C7—N2	1.279 (2)	C14—H14C	0.9600
C7—C8	1.450 (3)	O1—H1	0.8200
C7—H7	0.9300

C2—C1—H1A	109.5	C9—C8—C7	120.01 (16)
C2—C1—H1B	109.5	O1—C9—C8	122.83 (17)
H1A—C1—H1B	109.5	O1—C9—C10	117.82 (16)
C2—C1—H1C	109.5	C8—C9—C10	119.36 (17)
H1A—C1—H1C	109.5	O2—C10—C11	125.75 (17)
H1B—C1—H1C	109.5	O2—C10—C9	114.34 (17)
C6—C2—C3	116.38 (17)	C11—C10—C9	119.91 (18)
C6—C2—C1	121.39 (17)	C10—C11—C12	120.31 (18)
C3—C2—C1	122.22 (18)	C10—C11—H11	119.8
C4—C3—C2	119.25 (18)	C12—C11—H11	119.8
C4—C3—H3	120.4	C13—C12—C11	120.83 (18)
C2—C3—H3	120.4	C13—C12—H12	119.6
C3—C4—C5	119.68 (18)	C11—C12—H12	119.6
C3—C4—H4	120.2	C12—C13—C8	120.16 (17)
C5—C4—H4	120.2	C12—C13—H13	119.9
N1—C5—C4	122.84 (17)	C8—C13—H13	119.9
N1—C5—N2	119.77 (17)	O2—C14—H14A	109.5
C4—C5—N2	117.37 (17)	O2—C14—H14B	109.5
N1—C6—C2	125.65 (17)	H14A—C14—H14B	109.5
N1—C6—H6	117.2	O2—C14—H14C	109.5
C2—C6—H6	117.2	H14A—C14—H14C	109.5
N2—C7—C8	120.97 (17)	H14B—C14—H14C	109.5
N2—C7—H7	119.5	C5—N1—C6	116.19 (16)
C8—C7—H7	119.5	C7—N2—C5	121.88 (16)
C13—C8—C9	119.41 (17)	C9—O1—H1	109.5
C13—C8—C7	120.57 (17)	C10—O2—C14	117.02 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N2	0.82	1.84	2.5587 (19)	146
C3—H3···O2ⁱ	0.93	2.64	3.567 (3)	175
C4—H4···O1ⁱ	0.93	2.66	3.282 (2)	125

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₂O₂
M_r	242.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.5995 (6), 4.9546 (2), 23.9983 (12)
β (°)	117.6090
V (Å³)	1222.15 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.10 × 0.10

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.963, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	13275, 2806, 1822
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.198, 1.03
No. of reflections	2806
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), 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···N2	0.82	1.84	2.5587 (19)	146.0
C3—H3···O2ⁱ	0.93	2.64	3.567 (3)	175.3
C4—H4···O1ⁱ	0.93	2.66	3.282 (2)	124.7

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

The authors thank the National Basic Science Personnel Training Fund, administered by the Oceanographic Base of Ocean University of China, for its financial support for this project (grant No. J0730530).

References

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