2-[({2-[(2-Hy­droxy-5-meth­oxy­benzyl­idene)amino]­eth­yl}imino)­meth­yl]-4-meth­oxy­phenol

Abstract

The asymmetric unit of the title compound, C₁₈H₂₀N₂O₄, contains one-half mol­ecule with an inversion center located at the centroid of the mol­ecule. In the crystal, mol­ecules are linked by C—H⋯π inter­actions, forming layers parallel to (101). An intra­molecular O—H⋯N hydrogen bond also occurs.

Related literature  

For the synthesis of similar compounds see: Srinivasan et al. (1986 ▶); Moutet & Ourari (1997 ▶); Ourari et al. (2008 ▶).

Experimental  

Crystal data  

• C₁₈H₂₀N₂O₄

• M _r = 328.36

• Monoclinic,

• a = 15.0040 (12) Å

• b = 5.9722 (3) Å

• c = 9.3128 (8) Å

• β = 92.001 (3)°

• V = 833.98 (11) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 295 K

• 0.50 × 0.23 × 0.19 mm

Data collection  

• Nonius KappaCCD diffractometer

• 3001 measured reflections

• 1664 independent reflections

• 1097 reflections with I > 2σ(I)

• R _int = 0.021

Refinement  

• R[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 0.167

• S = 1.05

• 1664 reflections

• 111 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812018405/bq2353Isup3.cml

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

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

Cg is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯N2	0.82	1.85	2.5844 (18)	148
C10—H10C⋯Cgi	0.96	2.64	3.521 (2)	152

Symmetry code: (i) .

supplementary crystallographic information

Comment

The tetradentate Schiff base ligands derived from salicylaldehyde derivatives and diamino compounds have been found to be excellent chelating agents for most applications in coordination chemistry such as in catalysis (Srinivasan et al., 1986) and electrocatalysis (Moutet & Ourari, 1997; Ourari et al., 2008). Here, we report the synthesis of the title compound and its crystal structure.

The molecular structure of (I), and the atomic numbering used, is illustrated in Fig. 1. The asymmetric unit of the title compound, consists of one-half of the molecule, with the other half generated by a crystallographic inversion center. The crystal packing in the title structure can be described by a zigzag layers parallel to (101) plane (Fig. 2). There is one intramolecular O—H···N hydrogen bonding in this packing (Table 1, Fig. 2), which it is stabilized C—H···π and Van der Walls interactions (table 1) All these interactions link the molecules within the layers and also link the layers together and reinforcing the cohesion of the structure.

Experimental

60 mg of 1,2-diaminoethane (1 mmol) were dissolved in 10 ml of absolute ethanol. This solution was drop wise added, under stirring, to an ethanolic solution (10 ml) containing 304 mg of 5-methoxysalicylaldehyde (2 mmol). This mixture was refluxed for 1 h after which a yellow precipitate is formed, recovered by filtration, washed several times with diethyl oxide and dried to yield 282 mg (86%) of the title compound. The suitable crystals for X-ray analysis were obtained by slow evaporation from a mixture of solvents ethanol/dichloromethane (8/2, v/v).

Refinement

The H atoms were localized on Fourier maps but introduced in calculated positions and treated as riding on their parent atoms (C and O) with C—H = 0.93 Å (methine, aromatic), 0.96 Å (methyl), 0.97 Å (methylene) and O—H = 0.82 Å (hydroxyl) with U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

The molecular geometry of (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only the contents of the asymmetric unit are numbered.

Fig. 2.

Diagram of layered packing parallel to (101) plane and showing O—H···N and C—H···π interactions.

Crystal data

C18H20N2O4	F(000) = 348
Mr = 328.36	Dx = 1.308 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1761 reflections
a = 15.0040 (12) Å	θ = 1.0–26.4°
b = 5.9722 (3) Å	µ = 0.09 mm−1
c = 9.3128 (8) Å	T = 295 K
β = 92.001 (3)°	Prism, colorless
V = 833.98 (11) Å3	0.50 × 0.23 × 0.19 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	1097 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	Rint = 0.021
Graphite monochromator	θmax = 26.4°, θmin = 2.7°
Detector resolution: 9 pixels mm-1	h = −18→18
CCD rotation images, thick slices scans	k = −6→7
3001 measured reflections	l = −11→11
1664 independent reflections

Refinement

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)] = 0.054	H-atom parameters constrained
wR(F2) = 0.167	w = 1/[σ2(Fo2) + (0.101P)2 + 0.0006P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1664 reflections	Δρmax = 0.23 e Å−3
111 parameters	Δρmin = −0.16 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: 0.08 (2)

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	0.00544 (12)	0.5332 (3)	0.42227 (18)	0.0554 (5)
H1A	0.0237	0.404	0.3674	0.066*
H1B	−0.0511	0.586	0.3816	0.066*
C3	0.13689 (11)	0.6835 (3)	0.32973 (18)	0.0500 (5)
H3	0.1399	0.5537	0.2749	0.06*
C4	0.20642 (11)	0.8520 (3)	0.31789 (17)	0.0488 (5)
C5	0.20521 (13)	1.0483 (3)	0.40154 (19)	0.0545 (5)
C6	0.27360 (14)	1.2037 (3)	0.3894 (2)	0.0620 (5)
H6	0.2731	1.3341	0.4439	0.074*
C7	0.34154 (14)	1.1672 (3)	0.2983 (2)	0.0623 (5)
H7	0.3863	1.2739	0.2909	0.075*
C8	0.34469 (12)	0.9719 (3)	0.21605 (18)	0.0542 (5)
C9	0.27715 (11)	0.8166 (3)	0.22553 (18)	0.0515 (5)
H9	0.2784	0.687	0.1702	0.062*
C10	0.42592 (14)	0.7497 (3)	0.0532 (3)	0.0764 (7)
H10A	0.4313	0.6263	0.119	0.115*
H10B	0.4781	0.7572	−0.0033	0.115*
H10C	0.3742	0.7287	−0.0089	0.115*
N2	0.07208 (9)	0.7091 (2)	0.41315 (16)	0.0544 (5)
O5	0.13958 (10)	1.0889 (2)	0.49361 (15)	0.0712 (5)
H5	0.1037	0.9853	0.4903	0.107*
O8	0.41724 (10)	0.9514 (2)	0.13122 (15)	0.0727 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0480 (10)	0.0591 (10)	0.0594 (11)	−0.0045 (7)	0.0065 (8)	−0.0027 (8)
C3	0.0467 (10)	0.0539 (9)	0.0494 (10)	0.0010 (7)	0.0029 (8)	−0.0004 (7)
C4	0.0494 (10)	0.0483 (9)	0.0486 (10)	0.0007 (7)	0.0001 (8)	0.0034 (6)
C5	0.0598 (12)	0.0495 (10)	0.0541 (10)	0.0057 (8)	0.0025 (9)	0.0020 (7)
C6	0.0718 (13)	0.0466 (9)	0.0672 (12)	−0.0003 (8)	−0.0038 (10)	−0.0033 (8)
C7	0.0652 (12)	0.0518 (10)	0.0696 (12)	−0.0104 (8)	−0.0025 (10)	0.0063 (9)
C8	0.0517 (11)	0.0589 (10)	0.0521 (10)	−0.0062 (7)	0.0040 (8)	0.0086 (7)
C9	0.0546 (11)	0.0514 (9)	0.0488 (10)	−0.0030 (7)	0.0044 (9)	−0.0013 (7)
C10	0.0628 (13)	0.0883 (14)	0.0793 (15)	−0.0105 (10)	0.0209 (11)	−0.0118 (11)
N2	0.0486 (9)	0.0571 (9)	0.0578 (9)	−0.0012 (6)	0.0068 (7)	−0.0004 (6)
O5	0.0726 (10)	0.0631 (8)	0.0789 (10)	0.0062 (6)	0.0182 (8)	−0.0140 (6)
O8	0.0643 (9)	0.0764 (9)	0.0786 (10)	−0.0194 (7)	0.0215 (7)	−0.0033 (7)

Geometric parameters (Å, º)

C1—N2	1.455 (2)	C6—H6	0.93
C1—C1i	1.515 (3)	C7—C8	1.397 (2)
C1—H1A	0.97	C7—H7	0.93
C1—H1B	0.97	C8—O8	1.373 (2)
C3—N2	1.275 (2)	C8—C9	1.379 (2)
C3—C4	1.456 (2)	C9—H9	0.93
C3—H3	0.93	C10—O8	1.415 (2)
C4—C9	1.405 (2)	C10—H10A	0.96
C4—C5	1.408 (2)	C10—H10B	0.96
C5—O5	1.350 (2)	C10—H10C	0.96
C5—C6	1.391 (3)	O5—H5	0.82
C6—C7	1.366 (3)
N2—C1—C1i	109.99 (18)	C6—C7—C8	120.91 (16)
N2—C1—H1A	109.7	C6—C7—H7	119.5
C1i—C1—H1A	109.7	C8—C7—H7	119.5
N2—C1—H1B	109.7	O8—C8—C9	125.19 (16)
C1i—C1—H1B	109.7	O8—C8—C7	115.64 (15)
H1A—C1—H1B	108.2	C9—C8—C7	119.18 (17)
N2—C3—C4	121.80 (15)	C8—C9—C4	120.69 (16)
N2—C3—H3	119.1	C8—C9—H9	119.7
C4—C3—H3	119.1	C4—C9—H9	119.7
C9—C4—C5	119.26 (16)	O8—C10—H10A	109.5
C9—C4—C3	120.03 (15)	O8—C10—H10B	109.5
C5—C4—C3	120.68 (16)	H10A—C10—H10B	109.5
O5—C5—C6	119.26 (16)	O8—C10—H10C	109.5
O5—C5—C4	121.64 (16)	H10A—C10—H10C	109.5
C6—C5—C4	119.10 (17)	H10B—C10—H10C	109.5
C7—C6—C5	120.86 (16)	C3—N2—C1	119.31 (15)
C7—C6—H6	119.6	C5—O5—H5	109.5
C5—C6—H6	119.6	C8—O8—C10	117.41 (14)
N2—C3—C4—C9	179.47 (16)	C6—C7—C8—C9	1.2 (3)
N2—C3—C4—C5	1.4 (3)	O8—C8—C9—C4	178.87 (17)
C9—C4—C5—O5	−178.94 (15)	C7—C8—C9—C4	−0.8 (3)
C3—C4—C5—O5	−0.9 (3)	C5—C4—C9—C8	−0.2 (2)
C9—C4—C5—C6	0.8 (2)	C3—C4—C9—C8	−178.27 (15)
C3—C4—C5—C6	178.82 (15)	C4—C3—N2—C1	−178.95 (15)
O5—C5—C6—C7	179.38 (17)	C1i—C1—N2—C3	127.0 (2)
C4—C5—C6—C7	−0.3 (3)	C9—C8—O8—C10	−3.6 (3)
C5—C6—C7—C8	−0.7 (3)	C7—C8—O8—C10	176.06 (17)
C6—C7—C8—O8	−178.45 (17)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

Cg is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···N2	0.82	1.85	2.5844 (18)	148
C10—H10C···Cgii	0.96	2.64	3.521 (2)	152

Symmetry code: (ii) x, −y+1/2, z−3/2.