Crystal structure of (E)-4-meth­oxy-2-{[(5-methyl­pyridin-2-yl)imino]­meth­yl}phenol

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

doi:10.1107/S2056989015018113

organic compounds

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Crystal structure of (E)-4-methoxy-2-{[(5-methylpyridin-2-yl)imino]methyl}phenol

Farook Adam,^a ^* Md Azharul Arafath,^a Rosenani Anwaeul Haque ^a and Mohd Rizal Razali ^a

^aSchool of Chemical Sciences, 11800, USM Pulau Pinang, Malaysia
^*Correspondence e-mail: farook@usm.my

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 11 September 2015; accepted 28 September 2015; online 3 October 2015)

The molecule of the title Schiff base compound, C₁₄H₁₄N₂O₂, displays an E conformation with respect the imine C=N double bond. The molecule is approximately planar, with the dihedral angle formed by the planes of the pyridine and benzene rings being 5.72 (6)°. There is an intramolecular hydrogen bond involving the phenolic H and imine N atoms.

Keywords: crystal structure; Schiff base; N-heterocycle; intramolecular hydrogen bond.

CCDC reference: 1048553

1. Related literature

For the structure of related N-heterocyclic Schiff base compounds, see: Sahebalzamani et al. (2011 ); Rawat & Singh (2015 ); Thakar et al. (2015 ); Salam et al. (2011 ).

2. Experimental

2.1. Crystal data

C₁₄H₁₄N₂O₂
M_r = 242.27
Monoclinic P 2₁ /n
a = 12.7082 (12) Å
b = 4.7446 (4) Å
c = 21.124 (2) Å
β = 105.525 (2)°
V = 1227.21 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 K
0.41 × 0.35 × 0.12 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SABABS; Bruker, 2014 ) T_min = 0.030, T_max = 0.262
10950 measured reflections
2848 independent reflections
1910 reflections with I > 2σ(I)
R_int = 0.028

2.3. Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.151
S = 1.07
2848 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯N2	0.95 (2)	1.76 (3)	2.6276 (19)	150 (2)

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1048553

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018113/rz5166sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018113/rz5166Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015018113/rz5166Isup3.cml

checkCIF report

Comment top

The molecule of the title compound (Fig. 1) has an E configuration about the imine C═N double bond, as indicated by the value of 179.11(12° of the C5-N2-C6-C7 torsion angle. The molecule is is almost planar, with a dihedral angle between the pyridine and benzene rings of 5.72 (6)°. The molecular conformation is stabilized by an intramolecular O—H···N hydrogen bond (Table 1) occurring between the phenolic hydrogen and imine nitrogen atoms. In the crystal, packing is stabilized only by van der Waals interactions.

Related literature top

For the structure of related N-heterocyclic Schiff base compounds, see: Sahebalzamani et al. (2011); Rawat & Singh (2015); Thakar et al. (2015); Salam et al. (2011).

Experimental top

2-Hydroxy-5-methoxybenzaldehyde (5 mmol, 0.761 g) and 2-amino-5-methylpyridin (5 mmol, 0.541 g) were dissolved in ethanol in separate beakers, then the amine solution was added drop wise with stirring to the aldehyde in the round bottomed flask. Acetic acid was added and the solution was refluxed for 4 h under Ar atmosphere (Fig. 3). The solid product obtained was dried under reduced pressure overnight, then recrystallized with dichloromethane, diethyl ether and excess n-hexane, filtered, washed again with diethyl ether/n-hexane (1:3 v/v) and dried out over 24 h under reduced pressure in a desiccator. Purple single crystals of the title compound were grown on evaporation of an ethanol solution. M. p.: 380-381 K. Yield: 85%. Anal. calc. for C₁₄H₁₄N₂O₂ (FW: 242.28 g/mol): C, 69.43; H, 5.77; N, 11.55%. Found: C, 69.93; H, 5.69; N, 11.54%. IR (KBr pellets µ_max/cm^-1): 3427 ν(N—H), 2952 and 1384 ν(CH₃), 1618 ν(C═N), 1497 ν(C═C, ar.), 1210 ν(C—O), 1035 ν(C—N).

Structure description top

For the structure of related N-heterocyclic Schiff base compounds, see: Sahebalzamani et al. (2011); Rawat & Singh (2015); Thakar et al. (2015); Salam et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); 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 with displacement ellipsoids drawn at the 30% probability level. The dashed line indicates an intramolecular hydrogen bond.
	Fig. 2. Packing of the title compound compound viewed down the b axis.
	Fig. 3. Synthesis of the title compound.

(I) top

Crystal data top

C₁₄H₁₄N₂O₂	F(000) = 512
M_r = 242.27	D_x = 1.311 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 380 K
a = 12.7082 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 4.7446 (4) Å	θ = 1.7–27.6°
c = 21.124 (2) Å	µ = 0.09 mm⁻¹
β = 105.525 (2)°	T = 294 K
V = 1227.21 (19) Å³	Block, purple
Z = 4	0.41 × 0.35 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	1910 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.028
Absorption correction: multi-scan (SABABS; Bruker, 2014)	θ_max = 27.6°, θ_min = 1.7°
T_min = 0.030, T_max = 0.262	h = −16→14
10950 measured reflections	k = −6→6
2848 independent reflections	l = −27→27

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.0755P)² + 0.121P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2848 reflections	Δρ_max = 0.17 e Å⁻³
170 parameters	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₄H₁₄N₂O₂	V = 1227.21 (19) Å³
M_r = 242.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.7082 (12) Å	µ = 0.09 mm⁻¹
b = 4.7446 (4) Å	T = 294 K
c = 21.124 (2) Å	0.41 × 0.35 × 0.12 mm
β = 105.525 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2848 independent reflections
Absorption correction: multi-scan (SABABS; Bruker, 2014)	1910 reflections with I > 2σ(I)
T_min = 0.030, T_max = 0.262	R_int = 0.028
10950 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.17 e Å⁻³
2848 reflections	Δρ_min = −0.18 e Å⁻³
170 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.11027 (10)	0.5504 (3)	0.07471 (7)	0.0866 (5)
O2	0.52254 (10)	0.4026 (3)	0.24106 (6)	0.0762 (4)
N1	0.57565 (9)	−0.2914 (3)	0.07413 (6)	0.0527 (3)
N2	0.55236 (9)	0.0280 (3)	0.15589 (6)	0.0495 (3)
C1	0.63754 (12)	−0.4827 (3)	0.05470 (8)	0.0543 (4)
H1A	0.6101	−0.5632	0.0134	0.065*
C2	0.73934 (11)	−0.5698 (3)	0.09138 (7)	0.0476 (4)
C3	0.77704 (12)	−0.4503 (4)	0.15259 (8)	0.0558 (4)
H3A	0.8446	−0.5033	0.1797	0.067*
C4	0.71504 (12)	−0.2527 (4)	0.17389 (7)	0.0548 (4)
H4A	0.7403	−0.1707	0.2152	0.066*
C5	0.61512 (10)	−0.1780 (3)	0.13323 (7)	0.0445 (3)
C6	0.45685 (12)	0.0882 (3)	0.12034 (8)	0.0521 (4)
H6A	0.4309	−0.0023	0.0801	0.063*
C7	0.38731 (11)	0.2931 (3)	0.14055 (7)	0.0487 (4)
C8	0.42234 (12)	0.4410 (3)	0.19963 (7)	0.0536 (4)
C9	0.35180 (14)	0.6348 (4)	0.21589 (8)	0.0630 (5)
H9A	0.3750	0.7380	0.2545	0.076*
C10	0.24841 (14)	0.6764 (3)	0.17591 (9)	0.0621 (4)
H10A	0.2021	0.8053	0.1880	0.074*
C11	0.21273 (13)	0.5282 (4)	0.11786 (9)	0.0593 (4)
C12	0.28284 (12)	0.3399 (4)	0.10047 (8)	0.0583 (4)
H12A	0.2596	0.2422	0.0610	0.070*
C13	0.80422 (14)	−0.7829 (4)	0.06515 (9)	0.0651 (5)
H13A	0.8653	−0.8443	0.0999	0.098*	0.61 (2)
H13B	0.8302	−0.6989	0.0308	0.098*	0.61 (2)
H13C	0.7587	−0.9416	0.0479	0.098*	0.61 (2)
H13D	0.8763	−0.7110	0.0692	0.098*	0.39 (2)
H13E	0.7689	−0.8191	0.0197	0.098*	0.39 (2)
H13F	0.8090	−0.9547	0.0897	0.098*	0.39 (2)
C14	0.03899 (15)	0.7589 (5)	0.08715 (13)	0.0898 (7)
H14A	−0.0274	0.7588	0.0523	0.135*
H14B	0.0732	0.9404	0.0895	0.135*
H14C	0.0227	0.7192	0.1281	0.135*
H1O2	0.5562 (19)	0.261 (5)	0.2213 (13)	0.120 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0597 (7)	0.0913 (10)	0.1072 (10)	0.0322 (7)	0.0198 (7)	−0.0079 (8)
O2	0.0739 (8)	0.0858 (10)	0.0632 (7)	0.0210 (7)	0.0084 (6)	−0.0106 (7)
N1	0.0450 (6)	0.0544 (7)	0.0554 (7)	0.0084 (6)	0.0076 (5)	−0.0070 (6)
N2	0.0510 (7)	0.0454 (7)	0.0547 (7)	0.0090 (5)	0.0186 (5)	0.0028 (6)
C1	0.0491 (8)	0.0565 (9)	0.0558 (8)	0.0042 (7)	0.0113 (6)	−0.0122 (7)
C2	0.0453 (7)	0.0406 (7)	0.0595 (8)	0.0022 (6)	0.0182 (6)	0.0003 (7)
C3	0.0449 (7)	0.0614 (10)	0.0567 (8)	0.0126 (7)	0.0057 (6)	0.0021 (8)
C4	0.0527 (8)	0.0620 (10)	0.0461 (7)	0.0114 (7)	0.0067 (6)	−0.0049 (7)
C5	0.0448 (7)	0.0409 (7)	0.0494 (7)	0.0047 (6)	0.0151 (6)	0.0012 (6)
C6	0.0520 (8)	0.0489 (8)	0.0578 (8)	0.0094 (7)	0.0187 (7)	0.0000 (7)
C7	0.0524 (8)	0.0419 (7)	0.0576 (8)	0.0073 (6)	0.0247 (7)	0.0058 (7)
C8	0.0619 (9)	0.0489 (8)	0.0553 (8)	0.0079 (7)	0.0248 (7)	0.0076 (7)
C9	0.0803 (11)	0.0557 (9)	0.0618 (9)	0.0118 (9)	0.0342 (9)	−0.0001 (8)
C10	0.0730 (10)	0.0500 (9)	0.0774 (11)	0.0155 (8)	0.0448 (9)	0.0074 (8)
C11	0.0554 (9)	0.0545 (9)	0.0749 (10)	0.0134 (7)	0.0293 (8)	0.0078 (8)
C12	0.0557 (8)	0.0558 (9)	0.0663 (9)	0.0131 (8)	0.0213 (7)	−0.0019 (8)
C13	0.0633 (9)	0.0536 (9)	0.0842 (11)	0.0102 (8)	0.0297 (9)	−0.0057 (9)
C14	0.0614 (10)	0.0771 (13)	0.1362 (19)	0.0267 (10)	0.0357 (11)	0.0035 (13)

Geometric parameters (Å, º) top

O1—C11	1.379 (2)	C7—C12	1.388 (2)
O1—C14	1.413 (2)	C7—C8	1.397 (2)
O2—C8	1.3505 (19)	C8—C9	1.390 (2)
O2—H1O2	0.95 (3)	C9—C10	1.373 (2)
N1—C5	1.3282 (18)	C9—H9A	0.9300
N1—C1	1.3356 (18)	C10—C11	1.381 (2)
N2—C6	1.2771 (18)	C10—H10A	0.9300
N2—C5	1.4231 (17)	C11—C12	1.379 (2)
C1—C2	1.381 (2)	C12—H12A	0.9300
C1—H1A	0.9300	C13—H13A	0.9600
C2—C3	1.375 (2)	C13—H13B	0.9600
C2—C13	1.501 (2)	C13—H13C	0.9600
C3—C4	1.376 (2)	C13—H13D	0.9600
C3—H3A	0.9300	C13—H13E	0.9600
C4—C5	1.3754 (19)	C13—H13F	0.9600
C4—H4A	0.9300	C14—H14A	0.9600
C6—C7	1.4526 (19)	C14—H14B	0.9600
C6—H6A	0.9300	C14—H14C	0.9600

C11—O1—C14	118.00 (16)	C10—C9—H9A	119.4
C8—O2—H1O2	105.5 (15)	C8—C9—H9A	119.4
C5—N1—C1	117.31 (12)	C9—C10—C11	120.38 (14)
C6—N2—C5	119.06 (13)	C9—C10—H10A	119.8
N1—C1—C2	124.82 (14)	C11—C10—H10A	119.8
N1—C1—H1A	117.6	C12—C11—O1	115.88 (16)
C2—C1—H1A	117.6	C12—C11—C10	118.98 (16)
C3—C2—C1	116.25 (13)	O1—C11—C10	125.14 (14)
C3—C2—C13	122.49 (14)	C11—C12—C7	121.46 (16)
C1—C2—C13	121.26 (14)	C11—C12—H12A	119.3
C2—C3—C4	120.18 (13)	C7—C12—H12A	119.3
C2—C3—H3A	119.9	C2—C13—H13A	109.5
C4—C3—H3A	119.9	C2—C13—H13B	109.5
C5—C4—C3	119.02 (14)	H13A—C13—H13B	109.5
C5—C4—H4A	120.5	C2—C13—H13C	109.5
C3—C4—H4A	120.5	H13A—C13—H13C	109.5
N1—C5—C4	122.41 (13)	H13B—C13—H13C	109.5
N1—C5—N2	119.32 (12)	C2—C13—H13D	109.5
C4—C5—N2	118.27 (13)	C2—C13—H13E	109.5
N2—C6—C7	122.28 (14)	H13D—C13—H13E	109.5
N2—C6—H6A	118.9	C2—C13—H13F	109.5
C7—C6—H6A	118.9	H13D—C13—H13F	109.5
C12—C7—C8	119.25 (13)	H13E—C13—H13F	109.5
C12—C7—C6	119.06 (14)	O1—C14—H14A	109.5
C8—C7—C6	121.69 (14)	O1—C14—H14B	109.5
O2—C8—C9	119.18 (15)	H14A—C14—H14B	109.5
O2—C8—C7	122.08 (13)	O1—C14—H14C	109.5
C9—C8—C7	118.74 (15)	H14A—C14—H14C	109.5
C10—C9—C8	121.17 (16)	H14B—C14—H14C	109.5

C5—N1—C1—C2	−0.3 (2)	C12—C7—C8—O2	179.28 (14)
N1—C1—C2—C3	1.0 (2)	C6—C7—C8—O2	0.2 (2)
N1—C1—C2—C13	−178.93 (14)	C12—C7—C8—C9	−1.1 (2)
C1—C2—C3—C4	−0.9 (2)	C6—C7—C8—C9	179.78 (13)
C13—C2—C3—C4	178.97 (14)	O2—C8—C9—C10	−178.66 (14)
C2—C3—C4—C5	0.3 (2)	C7—C8—C9—C10	1.7 (2)
C1—N1—C5—C4	−0.5 (2)	C8—C9—C10—C11	−0.9 (2)
C1—N1—C5—N2	179.64 (12)	C14—O1—C11—C12	−174.24 (16)
C3—C4—C5—N1	0.5 (2)	C14—O1—C11—C10	6.3 (3)
C3—C4—C5—N2	−179.64 (13)	C9—C10—C11—C12	−0.6 (2)
C6—N2—C5—N1	3.8 (2)	C9—C10—C11—O1	178.92 (15)
C6—N2—C5—C4	−176.11 (13)	O1—C11—C12—C7	−178.37 (14)
C5—N2—C6—C7	179.11 (12)	C10—C11—C12—C7	1.2 (3)
N2—C6—C7—C12	−177.58 (14)	C8—C7—C12—C11	−0.3 (2)
N2—C6—C7—C8	1.5 (2)	C6—C7—C12—C11	178.81 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N2	0.95 (2)	1.76 (3)	2.6276 (19)	150 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N2	0.95 (2)	1.76 (3)	2.6276 (19)	150 (2)

Acknowledgements

The research was financially supported by the Third World Academy of Science (TWAS) and the RU grant 1001/PKIMIA/811269 from the Universiti Sains Malaysia.

References

Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (E)-4-meth­­oxy-2-{[(5-methyl­pyridin-2-yl)imino]­meth­yl}phenol

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of (E)-4-methoxy-2-{[(5-methylpyridin-2-yl)imino]methyl}phenol