Tris[2-(2-pyridylimino­meth­yl)phenol­ato(0.67−)]europium(III) nitrate

Qi-Hua Zhao; Hong-Yan Chen; Li-Nan Li; Ming-Jin Xie

doi:10.1107/S1600536809017206

. 2009 May 29;65(Pt 6):m697. doi: 10.1107/S1600536809017206

Tris[2-(2-pyridyliminomethyl)phenolato(0.67−)]europium(III) nitrate

Qi-Hua Zhao ^a,^*, Hong-Yan Chen ^a, Li-Nan Li ^a, Ming-Jin Xie ^a

PMCID: PMC2969734 PMID: 21583052

Abstract

The title compound, [Eu(C₁₂H_9.33N₂O)₃]NO₃, was obtained by the reaction of Eu(NO₃)·3H₂O and the Schiff base ligand 2-(2-pyridyliminomethyl)phenol. The Eu atom is located on a threefold rotation axis and is nine-coordinated by three tridentate Schiff base ligands in a distorted tricapped trigonal-prismatic geometry. The O atom at the phenol hydroxy group is partially deprotonated and the H atoms are modelled with one-third occupancy according to the space group R Inline graphic . Offset face-to-face π–π [centroid–centroid distance = 3.886 (3) Å] and edge-to-face C—H⋯π interactions are found between adjacent molecules. An intramolecular O—H⋯N hydrogen bond is also present.

Related literature

For the synthesis, see: Sreenivasulu et al. (2005 ▶); Henry et al. (2008 ▶). For related structures, see: Li & Zhang (2004 ▶); You et al. (2004 ▶).

Experimental

Crystal data

[Eu(C₁₂H_9.33N₂O)₃]NO₃
M _r = 806.61
Hexagonal,
a = 14.0398 (12) Å
c = 28.509 (5) Å
V = 4866.7 (11) Å³
Z = 6
Mo Kα radiation
μ = 1.99 mm⁻¹
T = 293 K
0.21 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.706, T _max = 0.819
10540 measured reflections
2599 independent reflections
1711 reflections with I > 2σ(I)
R _int = 0.092

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.128
S = 1.00
2599 reflections
155 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Data collection: APEX2 (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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017206/bq2130sup1.cif

e-65-0m697-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017206/bq2130Isup2.hkl

e-65-0m697-Isup2.hkl^{(128KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Eu1—O1	2.334 (4)
Eu1—N2	2.539 (5)
Eu1—N1	2.680 (5)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N2	0.89 (14)	2.09 (14)	2.783 (6)	134 (11)
C12—H12A⋯Cg1ⁱⁱⁱ	0.93	2.88	3.788 (9)	167

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Symmetry code: (iii) Inline graphic . Cg1 is the centroid of the C7–C12 benzene ring.

supplementary crystallographic information

Comment

During the last decades, considerable amount of work was devoted to the synthesis, structure and properties of transition metal complexes derived from Schiff bases because of their potential applications in catalysis and enzymatic reactions, magnetism and molecular architecture (Henry et al. 2008; Li & Zhang, 2004). Herein, we report the Schiff base complex mentioned in the title by solvent evaporation method (Sreenivasulu et al., 2005).

As shown in Fig. 1, the central Eu of the title compound is nine-coordinated. The coordination environment is defined by six N atoms and three O atoms from the three different N-Salicylidene-2-aminopyride ligands. (You et al., 2004). The bond length of Eu(1)—N(1) (2.681 (5) Å) and Eu(1)—N(2) (2.540 (5) Å) are longer than Eu(1)—O(1) (2.332 (4) Å). The bond angle of O(1)#1-Eu(1)—N(2)#2 (69.37 (14)°) is larger than N(2)#2-Eu(1)—N(1) (51.11 (15)°).

In one schiff base ligand, all of the atoms are almost in one plane. The most evident distortion is associated with the C12 atom, which is 0.2017 (3)Å away from the mean plane. Meanwhile, the two aromatic rings of the same ligand form a dihedral angle of 14.072 (4)°, and between every two neighbour ligands coordinated to the Eu, the schiff bases appear an angle of 80.768 (3), 80.292 (4), 80.933 (3)°, respectively. The phenyl ring and pyridine ring of adjacent molecules exist the offset face-to-face pi-pi stacking interactions, with a distance of 3.886 (3)Å (13.245 (4)°) and the edge-to-face C—H-pi interactions were founded between the two phenyl rings of adjacent molecules with the distance of 3.785 (5) Å. The intramolecular hydrogen-bonding was also found between O1 and N2 atoms with the N···O separation of 2.783 (6) Å.

Experimental

All chemicals used (reagent grade) were commercially available. Salicylaldehyde (0.122 g, 1 mmol) and 2-aminomethylpyridine (0.108 g, 1 mmol) were dissolved in ethanol (5 ml) respectively at room temperature. Then the two solutions were mixed and stirred slowly for about 30 min. Finally, the yellow ligand was synthesized. Then Eu(NO₃)₂.3H₂O (0.400 g, 1 mmol) in ethanol (5 ml) was added to it with stirring homogeneously. Yellow crystals suitable for X-ray ananlysis were obtained by slow evaporation at room temperature over several days.