2-Eth­oxy-6-[(methyl­imino)­meth­yl]phenol

Ge, C.M.; Zhang, S.-H.; Chao, F.; Wang, Y.G.; Li, W.

doi:10.1107/S1600536810019951

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1526

doi:10.1107/S1600536810019951

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2-Ethoxy-6-[(methylimino)methyl]phenol

Cheng Min Ge,^a Shu-Hua Zhang,^a ^* Feng Chao,^a Yin Guang Wang ^a and Wei Li ^a

^aCollege of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, People's Republic of China
^*Correspondence e-mail: zsh720108@163.com

(Received 9 May 2010; accepted 26 May 2010; online 5 June 2010)

In the title compound, C₁₀H₁₃NO₂, synthesized by the reaction of 2-hydroxy-3-ethoxybenzaldehyde with methylamine, there is an an intramolecular O—H⋯N hydrogen bond involving the hydroxy substituent and the amino N atom. In the crystal, molecules form inversion dimers connected by pairs of C—H⋯O hydrogen bonds.

Related literature

For similar Schiff bases, see: Chatziefthimiou et al. (2006 ); Zhang et al. (2003 ); Kargar et al. (2010 ). For related structures, see: Karadayı et al. (2003 ); Che et al. (2002 ); Jia et al. (2009 ); Fun et al. (2009 ). For structures with similar hydrogen-bonding to the title compound, see: Wang et al. (2010 ); Kargar et al. (2010).

Experimental

Crystal data

C₁₀H₁₃NO₂
M_r = 179.21
Monoclinic, P 2₁ /c
a = 9.2986 (19) Å
b = 14.713 (3) Å
c = 7.0551 (15) Å
β = 108.465 (8)°
V = 915.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.23 × 0.18 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
5022 measured reflections
1611 independent reflections
1338 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.085
wR(F²) = 0.277
S = 1.01
1611 reflections
122 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.92	2.616 (4)	142
C10—H10B⋯O1ⁱ	0.96	1.98	2.782 (4)	140
Symmetry code: (i) -x, -y, -z+1.

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810019951/su2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810019951/su2178Isup2.hkl

checkCIF report

Comment top

Schiff base compounds (Zhang et al., 2003; Karadayı et al., 2003; Che et al., 2002; Fun et al., 2009; Jia et al., 2009; Wang et al., 2010) have aroused increasing interest because of their antiviral, anticancer and antibacterial activities. Herein, we report the synthesis and crystal structure of the new title Schiff base compound, prepared by the reaction of 2-hydrogen-3-ethoxy-benzaldehyde and methylamine.

The molecular structure of the title molecule is illustrated in Fig. 1. The bond distances and angles are similar to those found in the methoxy analogue (Chatziefthimiou et al., 2006). Excluding the methyl groups (C8 and C10), all the other non-hydrogen atoms (O1/O2/N1/C1-C7/C9) lie in a plane (planar to within 0.054 (3)Å). There is an intramolecular O–H···N hydrogen bond between the phenol and imido-group (Table 1), similar to the situation in crystal structures of the methoxy analogue (Chatziefthimiou et al., 2006), 6-Acetoxymethyl-3-[(2-hydroxy-3-methoxybenzylidene)-amino]-3, 4,5,6-tetrahydro-2H-pyran-2,4,5-triyl triacetate (Wang et al., 2010) and 5,5'-Dimethoxy-2,2'-[4,5-dimethyl-o- phenylenebis(nitrilomethylidyne)]diphenol (Kargar et al., 2010).

In the crystal molecules are linked through weak intermolecular C–H···O hydrogen bond, to form dimers centered about an inversion center (Fig. 2).

Related literature top

For similar Schiff bases, see: Chatziefthimiou et al. (2006); Zhang et al. (2003); Kargar et al. (2010). For related structures, see: Karadayı et al. (2003); Che et al. (2002); Jia et al. (2009); Fun et al. (2009). For structures with similar hydrogen-bonding to the title compound, see: Wang et al. (2010); Kargar et al. (2010).

Experimental top

Compound 2-hydrogen-3-ethoxy-benzaldehyde (0.166 g, 1 mmol) was dissolved in ethanol (15 ml). To this solution was added a methylamine solution (0.5 ml) and the mixture was stirred and refluxed at 323 K for 2 h. After cooling to room temperature and filtration, the filtrate was left to stand at room temperature. Yellow block-like crystals, suitable for X-ray diffraction analysis, were obtained in a yield of 76 %. Analysis found (%): C 66.97, H 7.38, N 7.84; C₁₀H₁₃NO₂ requires (%): C 67.02, H 7.31, N 7.82.

Computing details top

Data collection: SMART (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: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, showing 30 % probability displacement ellipsoids. The intramolecular O-H···N hydrogen bond is shown as a dashed red line.
	Fig. 2. A view along the c-axis of the crystal packing of the title compound. The O-H···N and C-H···O hydrogen bonds are shown as dashed lines.

2-Ethoxy-6-[(methylimino)methyl]phenol top

Crystal data top

C₁₀H₁₃NO₂	F(000) = 384
M_r = 179.21	D_x = 1.300 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1611 reflections
a = 9.2986 (19) Å	θ = 2.3–25.0°
b = 14.713 (3) Å	µ = 0.09 mm⁻¹
c = 7.0551 (15) Å	T = 296 K
β = 108.465 (8)°	Block, yellow
V = 915.5 (3) Å³	0.23 × 0.18 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1338 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
phi and ω scans	h = −10→11
5022 measured reflections	k = −17→17
1611 independent reflections	l = −8→6

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.085	H-atom parameters constrained
wR(F²) = 0.277	w = 1/[σ²(F_o²) + (0.1633P)² + 1.1252P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
1611 reflections	Δρ_max = 0.86 e Å⁻³
122 parameters	Δρ_min = −0.58 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (11)

Crystal data top

C₁₀H₁₃NO₂	V = 915.5 (3) Å³
M_r = 179.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2986 (19) Å	µ = 0.09 mm⁻¹
b = 14.713 (3) Å	T = 296 K
c = 7.0551 (15) Å	0.23 × 0.18 × 0.15 mm
β = 108.465 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1338 reflections with I > 2σ(I)
5022 measured reflections	R_int = 0.028
1611 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.085	0 restraints
wR(F²) = 0.277	H-atom parameters constrained
S = 1.01	Δρ_max = 0.86 e Å⁻³
1611 reflections	Δρ_min = −0.58 e Å⁻³
122 parameters

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.

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	−0.0203 (4)	0.1015 (2)	0.8638 (5)	0.0465 (9)
C2	−0.1745 (4)	0.0879 (2)	0.8267 (5)	0.0477 (9)
C3	−0.2406 (4)	0.1178 (3)	0.9696 (6)	0.0592 (10)
H3	−0.3434	0.1084	0.9482	0.071*
C4	−0.1544 (5)	0.1603 (3)	1.1393 (6)	0.0654 (11)
H4	−0.2000	0.1813	1.2308	0.078*
C5	0.0000 (5)	0.1728 (3)	1.1776 (6)	0.0578 (10)
H5	0.0577	0.2010	1.2952	0.069*
C6	0.0682 (4)	0.1432 (2)	1.0401 (5)	0.0481 (9)
C7	0.3157 (4)	0.1927 (3)	1.2361 (6)	0.0579 (10)
H7A	0.3057	0.1632	1.3542	0.069*
H7B	0.2889	0.2563	1.2391	0.069*
C8	0.4756 (5)	0.1841 (4)	1.2314 (7)	0.0727 (12)
H8A	0.4942	0.1223	1.2015	0.109*
H8B	0.5451	0.2007	1.3592	0.109*
H8C	0.4897	0.2236	1.1304	0.109*
C9	−0.2684 (4)	0.0421 (3)	0.6471 (5)	0.0535 (9)
H9	−0.3714	0.0343	0.6271	0.064*
C10	−0.3148 (3)	−0.0314 (2)	0.3564 (4)	0.0407 (8)
H10A	−0.3663	−0.0781	0.4052	0.061*
H10B	−0.2616	−0.0583	0.2741	0.061*
H10C	−0.3875	0.0116	0.2792	0.061*
N1	−0.2115 (3)	0.0129 (2)	0.5180 (5)	0.0556 (9)
O1	0.0527 (3)	0.0762 (2)	0.7326 (4)	0.0612 (9)
H1	−0.0096	0.0596	0.6275	0.092*
O2	0.2187 (3)	0.15026 (19)	1.0599 (4)	0.0590 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0514 (19)	0.0426 (17)	0.0509 (19)	0.0052 (14)	0.0240 (15)	0.0028 (14)
C2	0.0478 (19)	0.0433 (17)	0.054 (2)	0.0058 (14)	0.0193 (15)	0.0042 (14)
C3	0.052 (2)	0.063 (2)	0.070 (2)	0.0072 (17)	0.0295 (18)	−0.0009 (19)
C4	0.065 (2)	0.075 (3)	0.067 (2)	0.0070 (19)	0.036 (2)	−0.013 (2)
C5	0.063 (2)	0.058 (2)	0.057 (2)	0.0007 (17)	0.0261 (18)	−0.0085 (17)
C6	0.0512 (19)	0.0442 (17)	0.0526 (19)	0.0023 (14)	0.0215 (16)	−0.0013 (14)
C7	0.057 (2)	0.061 (2)	0.056 (2)	−0.0070 (17)	0.0180 (17)	−0.0089 (17)
C8	0.055 (2)	0.091 (3)	0.070 (3)	−0.003 (2)	0.018 (2)	−0.005 (2)
C9	0.0439 (18)	0.059 (2)	0.058 (2)	0.0032 (15)	0.0174 (16)	0.0038 (17)
C10	0.0279 (14)	0.0597 (19)	0.0317 (15)	−0.0057 (12)	0.0057 (11)	−0.0128 (13)
N1	0.0500 (17)	0.0607 (19)	0.0542 (18)	−0.0019 (13)	0.0140 (15)	−0.0045 (14)
O1	0.0486 (15)	0.0812 (19)	0.0581 (16)	−0.0025 (13)	0.0229 (12)	−0.0191 (13)
O2	0.0493 (15)	0.0723 (17)	0.0597 (16)	−0.0071 (12)	0.0233 (12)	−0.0153 (12)

Geometric parameters (Å, º) top

C1—O1	1.362 (4)	C7—C8	1.503 (6)
C1—C2	1.388 (5)	C7—H7A	0.9700
C1—C6	1.398 (5)	C7—H7B	0.9700
C2—C3	1.406 (5)	C8—H8A	0.9600
C2—C9	1.457 (5)	C8—H8B	0.9600
C3—C4	1.364 (6)	C8—H8C	0.9600
C3—H3	0.9300	C9—N1	1.264 (5)
C4—C5	1.387 (6)	C9—H9	0.9300
C4—H4	0.9300	C10—N1	1.398 (4)
C5—C6	1.386 (5)	C10—H10A	0.9600
C5—H5	0.9300	C10—H10B	0.9600
C6—O2	1.366 (4)	C10—H10C	0.9600
C7—O2	1.428 (4)	O1—H1	0.8200

O1—C1—C2	122.7 (3)	O2—C7—H7B	110.2
O1—C1—C6	116.4 (3)	C8—C7—H7B	110.2
C2—C1—C6	120.8 (3)	H7A—C7—H7B	108.5
C1—C2—C3	118.7 (3)	C7—C8—H8A	109.5
C1—C2—C9	121.9 (3)	C7—C8—H8B	109.5
C3—C2—C9	119.4 (3)	H8A—C8—H8B	109.5
C4—C3—C2	120.3 (3)	C7—C8—H8C	109.5
C4—C3—H3	119.9	H8A—C8—H8C	109.5
C2—C3—H3	119.9	H8B—C8—H8C	109.5
C3—C4—C5	121.1 (3)	N1—C9—C2	120.8 (3)
C3—C4—H4	119.5	N1—C9—H9	119.6
C5—C4—H4	119.5	C2—C9—H9	119.6
C6—C5—C4	119.8 (4)	N1—C10—H10A	109.5
C6—C5—H5	120.1	N1—C10—H10B	109.5
C4—C5—H5	120.1	H10A—C10—H10B	109.5
O2—C6—C5	125.8 (3)	N1—C10—H10C	109.5
O2—C6—C1	114.8 (3)	H10A—C10—H10C	109.5
C5—C6—C1	119.3 (3)	H10B—C10—H10C	109.5
O2—C7—C8	107.5 (3)	C9—N1—C10	114.2 (3)
O2—C7—H7A	110.2	C1—O1—H1	109.5
C8—C7—H7A	110.2	C6—O2—C7	117.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.92	2.616 (4)	142
C10—H10B···O1ⁱ	0.96	1.98	2.782 (4)	140

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃NO₂
M_r	179.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.2986 (19), 14.713 (3), 7.0551 (15)
β (°)	108.465 (8)
V (Å³)	915.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5022, 1611, 1338
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.085, 0.277, 1.01
No. of reflections	1611
No. of parameters	122
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.58

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), 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···N1	0.82	1.92	2.616 (4)	142
C10—H10B···O1ⁱ	0.96	1.98	2.782 (4)	140

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

We acknowledge financial support by the Guangxi Key Laboratory for Advanced Materials and New Preparation Technology (No.0842003–25), the Young Science Foundation of Guangxi Province of China (No. 0832085) and the start-up foundation for doctoral students of Guilin University of Technology.

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