{μ-6,6′-Dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methyl­idyne)]diphenolato}-μ-nitrato-dinitratoterbium(III)zinc(II)

Jing-Rong Chen; Yan Sui; Li Chen; Ji-Wu Wen; Li-Yang Yin

doi:10.1107/S1600536808006958

This article has been retracted.

Retraction in: Acta Crystallogr Sect E Struct Rep Online. 2010 Mar 17;66(Pt 4):e21 See also: PMC Retraction Policy

. 2008 Mar 20;64(Pt 4):m562–m563. doi: 10.1107/S1600536808006958

{μ-6,6′-Dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}-μ-nitrato-dinitratoterbium(III)zinc(II)

Jing-Rong Chen ^a, Yan Sui ^b,^*, Li Chen ^c, Ji-Wu Wen ^b, Li-Yang Yin ^b

PMCID: PMC2961047 PMID: 21202018

Abstract

In the title heteronuclear Zn^II—Tb^III complex (systematic name: {6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato-1κ⁴ O ⁶,O ¹,O ^1′,O ^6′}:2κ⁴ O ¹,N,N′,O ^1′-μ-nitrato-1:2κ² O:O′-dinitrato-1κ⁴ O,O′-terbium(III)zinc(II)), [TbZn(C₁₈H₁₈N₂O₄)(NO₃)₃], with the hexadentate Schiff base compartmental ligand N,N′-bis(3-methoxysalicylidene)ethylenediamine (H₂ L), the Tb and Zn atoms are triply bridged by two phenolate O atoms of the Schiff base ligand and one nitrate ion. The five-coordinate Zn atom is in a square-pyramidal geometry with the donor centers of two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The Tb^III center has a ninefold coordination environment of O atoms, involving the phenolate O atoms, two methoxy O atoms, two O atoms from two nitrate ions and one from the bridging nitrate ion. Weak intermolecular C—H⋯O interactions generate a two-dimensional layer structure.

Related literature

For related literature, see: Baggio et al. (2000 ▶); Caravan et al. (1999 ▶); Edder et al. (2000 ▶); Knoer et al. (2005 ▶); Sui et al. (2006 ▶, 2007 ▶).

Experimental

Crystal data

[TbZn(C₁₈H₁₈N₂O₄)(NO₃)₃]
M _r = 736.66
Monoclinic,
a = 10.6818 (4) Å
b = 16.5022 (6) Å
c = 14.9546 (6) Å
β = 99.618 (1)°
V = 2599.04 (17) Å³
Z = 4
Mo Kα radiation
μ = 3.69 mm⁻¹
T = 293 (2) K
0.33 × 0.22 × 0.12 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.375, T _max = 0.666
15507 measured reflections
4431 independent reflections
3722 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.068
S = 1.00
4431 reflections
345 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: APEX2; software used to prepare material for publication: APEX2 and publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006958/at2549sup1.cif

e-64-0m562-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006958/at2549Isup2.hkl

e-64-0m562-Isup2.hkl^{(217.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Tb1—O1	2.310 (2)
Tb1—O2	2.307 (2)
Tb1—O3	2.606 (2)
Tb1—O4	2.606 (2)
Tb1—O5	2.335 (3)
Tb1—O8	2.498 (3)
Tb1—O9	2.464 (3)
Tb1—O11	2.444 (3)
Tb1—O12	2.472 (3)
Zn1—O1	2.021 (2)
Zn1—O2	2.007 (2)
Zn1—O6	1.978 (3)
Zn1—N1	2.030 (3)
Zn1—N2	2.046 (3)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O11ⁱ	0.93	2.45	3.376 (5)	173
C9—H9A⋯O13ⁱⁱ	0.97	2.54	3.487 (6)	165

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We gratefully acknowledge financial support from the Department of Education, JiangXi Province (No. 2007317) and the Natural Science Foundation of JiangXi Province (No: 2007GZH1667).

supplementary crystallographic information

Comment

The potential applications of trivalent lanthanide complexes as contrast agent for magnetic resonance imaging and stains for fluorescence imaging have prompted considerable interest in the preparation, magnetic and optical properties of 3 d-4f hetorometallic dinuclear complexes (Baggio et al., 2000; Caravan et al., 1999; Edder et al., 2000; Knoer et al., 2005). As part of our investigations into the structure and applications of 3 d-4f hetorometallic Schiff base complexes (Sui et al. 2006; Sui et al. 2007), we report here the synthesis and X-ray crystal structure analysis of the title complex, (I), a new Zn^II—Tb^III complex with salen-type Schiff base N,N'-bis(3-methoxysalicylidene) ethylenediamine (H₂L).

Complex (I) crystallizes in the space group P2₁/n, with zinc and terbium triply bridged by two phenolate O atoms provided by the Schiff base ligand and one nitrate ion. The inner salen-type cavity is occupied by zinc(II), while terbium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand.

The Tb^III center has a ninefold coordination environment of O atoms, involving the phenolate O atoms, two methoxy O atoms, two O atoms from two nitrate ions and one from the bridging nitrate ion. The four kinds of Tb—O bond distances are significantly different, the longest being the Tb—O (methoxy) separations and the shortest being the Tb—O (phenolate) and Tb—O5 (bridging nitrate).

The Zn^II is in a square-pyramidal geometry and is five-coordinated by two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The Zn atom is 0.6062 (4) Å above the mean N₂O₂ plane with an average deviation from the plane of 0.0383 (3) Å, which construct the bottom of square-pyramid. The Zn—O6 (bridging nitrate) separation is 1.978 (3)Å and the angles of this Zn—O vector with the Zn—N or Zn—O bonds lie between 102.5 (5)° and 112.7 (6)°, which suggesting that the Zn^II is in a slightly distorted square-pyramidal conformation.

Adjacent molecules are held together by weak interactions (C5—H5···O11ⁱ= 3.376 (5) Å and C9—H9A···O13ⁱⁱ= 3.487 (6) Å; symmetry codes: (i) 1/2 + x, 1/2 - y, -1/2 + z; (ii) 1 - x, -y, 1 - z). These link the molecules into a two-dimensional layer structure (Fig 2).

Experimental

H₂L was prepared by the 2:1 condensation of 3-methoxysalicylaldehyde and ethylenediamine in methanol. Complex (I) was obtained by the treatment of zinc(II) acetate dihydrate (0.188 g, 1 mmol) with H₂L (0.328 g, 1 mmol) in methanol solution (80 ml) under reflux for 3 h and then for another 3 h after the addition of terbium(III) nitrate hexahydrate (0.453 g, 1 mmol). The reaction mixture was cooled and the resulting precipitate was filtered off, washed with diethyl ether and dried in vacuo. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation at room temperature of a methanol solution. Analysis calculated for C₁₈H₁₈N₅O₁₃TbZn: C 29.35 H 2.46, N 9.51, Tb 21.57, Zn 8.88%; found: C 29.40, H 2.45, N 9.53, Tb 21.60, Zn 8.906%. IR (KBr, cm^-1): 1640 (C=N), 1386,1490(nitrate).