(E)-2-[(2-Hydroxy­ethyl)iminiometh­yl]-6-methoxy­phenolate

Abstract

The title Schiff base compound, C₁₀H₁₃NO₃, obtained by the reaction of 2-hydr­oxy-3-methoxy­benzaldehyde and 2-amino­ethanol in methanol solution, crystallizes in a zwitterionic form, in which the mol­ecule adopts a trans configuration about the central C=N bond. An intra­molecular N—H⋯O hydrogen bond occurs. In the crystal structure, mol­ecules are linked into chains by inter­molecular O—H⋯O hydrogen bonding.

Related literature

For related structures, see: Cui et al. (1999 ▶); Dong et al. (2007 ▶); Li et al. (2005 ▶); Ng (2008 ▶); Oshio et al. (2003 ▶); Sun et al. (2006 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₀H₁₃NO₃

• M _r = 195.21

• Orthorhombic,

• a = 14.148 (6) Å

• b = 6.587 (3) Å

• c = 10.760 (4) Å

• V = 1002.8 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 295 K

• 0.30 × 0.30 × 0.12 mm

Data collection

• Bruker SMART APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.974, T _max = 0.991

• 7345 measured reflections

• 1041 independent reflections

• 923 reflections with I > 2σ(I)

• R _int = 0.037

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.084

• S = 1.07

• 1041 reflections

• 127 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.09 e Å⁻³

• Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.95	2.617 (2)	134
O3—H3⋯O1i	0.82	1.95	2.741 (3)	161

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound, (I), derived from 3-methoxy-2-hydroxybenzaldehyde and 2-aminoethanol, is a potential NO₃ tetradentate Schiff base ligand and its complexes with Cd(II), Cu(II), Zn(II) and Fe(III) have been reported (Cui et al., 1999; Dong et al., 2007; Li et al., 2005; Oshio et al., 2003). Here, the structure of (I) is described.

The title molecule exists in a zwitterionic form with a strong intramolecular N—H···O hydrogen bond (Table 1) between the NH⁺ and the phenolate O^-, as shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al.,1987). The N1=C8 [1.294 (3) Å] and N1—C8 [1.453 (3) Å] bond distances are comparable to these found in similar Schiff base compounds, such as 2,4-Dibromo-6-(2-hydroxyethyliminiomethyl)- phenolate [1.277 (5) and 1.451 (4) Å] (Sun et al., 2006) and 4-chloro-2-[tris(hydroxymethyl)methyliminiomethyl]phenolate [1.288 (2) and 1.467 (2) Å] (Ng, 2008). As expected, the molecule adopts a trans configuration about the central C=N bond. In the crystal structure, O3—H3···O1ⁱ (symmetry code as given in Table 1) intermolecular hydrogen bonds formed between the hydroxy and oxygen of phenolate link the molecules into a one-dimension supramolecular chain.

Experimental

3-Methoxy-2-hydroxybenzaldehyde (0.152 g, 1 mmol) and equimolar 2-aminoethanol (0.061 g, 1 mmol) were refluxed for 30 min in methanol solution (15 ml). The reaction mixtures were cooled to room temprature and filtered. After keeping the filtrate in air for 3 d, yellow blocks of (I) (yield 66%; mp 338–339 K) were obtained.

Refinement

H atoms were placed at calculated positions and refined in the riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2Ueq(C) for sp² H atoms, C—H = 0.96 Å and U_iso(H) = 1.5Ueq(C) for methyl H atoms, C—H = 0.97 Å and U_iso(H) = 1.2Ueq(C) for methylene H atoms, N—H = 0.86 Å and U_iso(H) = 1.2Ueq(C) for imino group, and O—H = 0.82 Å and U_iso(H) = 1.5Ueq(C) for hydroxy. Friedel pairs were merged.

Figures

Fig. 1.

The structure of (I) with displacement ellipsoids drawn at the 50% probability level. The N—H···O hydrogen bond is shown as a dashed line.

Crystal data

C10H13NO3	F(000) = 416
Mr = 195.21	Dx = 1.293 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1828 reflections
a = 14.148 (6) Å	θ = 2.9–20.4°
b = 6.587 (3) Å	µ = 0.10 mm−1
c = 10.760 (4) Å	T = 295 K
V = 1002.8 (7) Å3	Block, yellow
Z = 4	0.30 × 0.30 × 0.12 mm

Data collection

Bruker APEX CCD diffractometer	1041 independent reflections
Radiation source: fine-focus sealed tube	923 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −17→17
Tmin = 0.974, Tmax = 0.991	k = −8→8
7345 measured reflections	l = −12→13

Refinement

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0473P)2 + 0.0337P] where P = (Fo2 + 2Fc2)/3
1041 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.09 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.53278 (16)	0.7444 (3)	0.0860 (2)	0.0408 (5)
C2	0.57651 (16)	0.9338 (3)	0.0535 (2)	0.0451 (6)
C3	0.69788 (18)	1.1717 (4)	0.1022 (3)	0.0718 (9)
H3A	0.6519	1.2763	0.1164	0.108*
H3B	0.7207	1.1807	0.0183	0.108*
H3C	0.7497	1.1885	0.1588	0.108*
C4	0.5396 (2)	1.0535 (4)	−0.0390 (3)	0.0557 (7)
H4	0.5680	1.1776	−0.0566	0.067*
C5	0.4599 (2)	0.9927 (5)	−0.1078 (3)	0.0625 (8)
H5	0.4366	1.0750	−0.1710	0.075*
C6	0.41744 (18)	0.8135 (4)	−0.0814 (3)	0.0570 (7)
H6	0.3655	0.7718	−0.1278	0.068*
C7	0.45145 (15)	0.6891 (4)	0.0160 (2)	0.0436 (5)
C8	0.39971 (16)	0.5130 (4)	0.0485 (2)	0.0460 (6)
H8	0.3479	0.4790	−0.0006	0.055*
C9	0.36073 (17)	0.2262 (4)	0.1804 (3)	0.0535 (6)
H9A	0.4005	0.1091	0.1961	0.064*
H9B	0.3173	0.1915	0.1140	0.064*
C10	0.30532 (16)	0.2758 (4)	0.2962 (3)	0.0529 (6)
H10A	0.2717	0.1553	0.3232	0.064*
H10B	0.3490	0.3137	0.3617	0.064*
N1	0.41934 (14)	0.3958 (3)	0.1415 (2)	0.0478 (5)
H1	0.4701	0.4199	0.1829	0.057*
O1	0.56592 (11)	0.6322 (2)	0.17429 (18)	0.0486 (4)
O2	0.65545 (11)	0.9784 (3)	0.1213 (2)	0.0564 (5)
O3	0.23996 (12)	0.4345 (2)	0.2785 (2)	0.0584 (5)
H3	0.1946	0.3924	0.2387	0.088*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0358 (11)	0.0387 (12)	0.0478 (13)	0.0046 (9)	0.0063 (10)	−0.0074 (11)
C2	0.0393 (12)	0.0407 (13)	0.0553 (16)	0.0030 (10)	0.0127 (11)	−0.0106 (12)
C3	0.0623 (17)	0.0421 (15)	0.111 (3)	−0.0143 (14)	0.0175 (19)	−0.0154 (16)
C4	0.0608 (17)	0.0435 (14)	0.0629 (17)	0.0038 (13)	0.0206 (15)	0.0050 (13)
C5	0.0670 (18)	0.0703 (19)	0.0502 (16)	0.0090 (15)	0.0064 (14)	0.0132 (15)
C6	0.0507 (14)	0.0726 (18)	0.0477 (15)	0.0022 (13)	−0.0017 (12)	0.0014 (14)
C7	0.0378 (12)	0.0484 (13)	0.0445 (13)	0.0014 (11)	0.0028 (10)	−0.0071 (12)
C8	0.0341 (12)	0.0521 (14)	0.0520 (14)	0.0004 (10)	−0.0026 (11)	−0.0117 (12)
C9	0.0420 (13)	0.0424 (13)	0.0760 (18)	−0.0020 (10)	−0.0002 (14)	0.0002 (13)
C10	0.0422 (12)	0.0533 (15)	0.0633 (16)	0.0033 (11)	−0.0071 (12)	0.0138 (13)
N1	0.0354 (10)	0.0481 (12)	0.0600 (14)	−0.0036 (9)	−0.0025 (9)	−0.0050 (11)
O1	0.0400 (8)	0.0440 (9)	0.0619 (11)	−0.0040 (7)	−0.0082 (8)	0.0003 (9)
O2	0.0436 (9)	0.0433 (9)	0.0822 (14)	−0.0083 (8)	0.0020 (9)	−0.0062 (9)
O3	0.0410 (9)	0.0591 (10)	0.0750 (13)	0.0088 (9)	−0.0069 (9)	−0.0038 (10)

Geometric parameters (Å, °)

C1—O1	1.291 (3)	C6—H6	0.9300
C1—C7	1.423 (3)	C7—C8	1.416 (3)
C1—C2	1.436 (3)	C8—N1	1.294 (3)
C2—O2	1.366 (3)	C8—H8	0.9300
C2—C4	1.373 (4)	C9—N1	1.453 (3)
C3—O2	1.422 (3)	C9—C10	1.508 (4)
C3—H3A	0.9600	C9—H9A	0.9700
C3—H3B	0.9600	C9—H9B	0.9700
C3—H3C	0.9600	C10—O3	1.409 (3)
C4—C5	1.407 (4)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
C5—C6	1.355 (4)	N1—H1	0.8600
C5—H5	0.9300	O3—H3	0.8200
C6—C7	1.415 (4)
O1—C1—C7	122.5 (2)	C6—C7—C1	121.3 (2)
O1—C1—C2	121.3 (2)	C8—C7—C1	119.8 (2)
C7—C1—C2	116.2 (2)	N1—C8—C7	124.6 (2)
O2—C2—C4	125.1 (2)	N1—C8—H8	117.7
O2—C2—C1	114.1 (2)	C7—C8—H8	117.7
C4—C2—C1	120.8 (2)	N1—C9—C10	111.6 (2)
O2—C3—H3A	109.5	N1—C9—H9A	109.3
O2—C3—H3B	109.5	C10—C9—H9A	109.3
H3A—C3—H3B	109.5	N1—C9—H9B	109.3
O2—C3—H3C	109.5	C10—C9—H9B	109.3
H3A—C3—H3C	109.5	H9A—C9—H9B	108.0
H3B—C3—H3C	109.5	O3—C10—C9	113.0 (2)
C2—C4—C5	121.5 (2)	O3—C10—H10A	109.0
C2—C4—H4	119.2	C9—C10—H10A	109.0
C5—C4—H4	119.2	O3—C10—H10B	109.0
C6—C5—C4	119.5 (3)	C9—C10—H10B	109.0
C6—C5—H5	120.2	H10A—C10—H10B	107.8
C4—C5—H5	120.2	C8—N1—C9	124.0 (2)
C5—C6—C7	120.6 (3)	C8—N1—H1	118.0
C5—C6—H6	119.7	C9—N1—H1	118.0
C7—C6—H6	119.7	C2—O2—C3	117.4 (2)
C6—C7—C8	118.8 (2)	C10—O3—H3	109.5
O1—C1—C2—O2	1.6 (3)	C2—C1—C7—C6	1.1 (3)
C7—C1—C2—O2	−178.65 (19)	O1—C1—C7—C8	4.8 (3)
O1—C1—C2—C4	−178.8 (2)	C2—C1—C7—C8	−175.0 (2)
C7—C1—C2—C4	1.0 (3)	C6—C7—C8—N1	−174.5 (2)
O2—C2—C4—C5	177.5 (2)	C1—C7—C8—N1	1.8 (3)
C1—C2—C4—C5	−2.1 (3)	N1—C9—C10—O3	63.7 (3)
C2—C4—C5—C6	1.0 (4)	C7—C8—N1—C9	174.2 (2)
C4—C5—C6—C7	1.2 (4)	C10—C9—N1—C8	−104.5 (3)
C5—C6—C7—C8	174.0 (2)	C4—C2—O2—C3	5.8 (3)
C5—C6—C7—C1	−2.2 (4)	C1—C2—O2—C3	−174.6 (2)
O1—C1—C7—C6	−179.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.95	2.617 (2)	134
O3—H3···O1i	0.82	1.95	2.741 (3)	161

Symmetry codes: (i) x−1/2, −y+1, z.