Issue 20, 2010
From the journal:

Dalton Transactions

Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation†

Emilio Pardo,a   Cyrille Train,ab   Rodrigue Lescouëzec,a   Kamal Boubekeur,a   Eliseo Ruiz,c   Francesc Lloretd  and  Michel Verdaguer*a  

* Corresponding authors

a Institut Parisien de Chimie Moléculaire, Université Pierre et Marie Curie-Paris 6, UMR 7201, Paris, France
E-mail: Michel.verdaguer@upmc.fr
Fax: 00 33 1 44 27 38 41
Tel: 00 33 1 44 27 30 59

b Laboratoire National des Champs Magnétiques Intenses, UPR CNRS 3228, 25 rue des Martyrs, B.P. 166, Grenoble cedex 9, France; Université Joseph Fourier, BP 53, F-38041 Grenoble Cedex 9, France

c Departament de Química Inorgànica and Institut de Recerca de Química Teòrica i Computacional, Universitat de Barcelona, Diagonal 647, Spain

d Departament de Química Inorgànica, Instituto de Ciencia Molecular (ICMOL). Universitat de València, Paterna, València, Spain

Abstract

Two isostructural heterometallic trinuclear oxalato-bridged complexes of formula C4[MCr2(ox)6(H2O)2]·nH2O (C+ = 4-aminopyridinium; ox2− = oxalate dianion; M2+ = Mn2+, n = 3, 1; M2+ = Co2+, n = 3.25, 2) have been synthesized by using direct self-assembly methods combining C3[Cr(ox)3] and the chloride salts of the corresponding metal ion. The crystal structures of both compounds have been resolved by single-crystal X-ray diffraction. They crystallize in the C2/c space group [a = 11.5113(15) Å, b = 20.250(3) Å, c = 21.810(4) Å, β = 100.447(10)°, V = 5161.6(3) Å3, and Z = 4 for 1, and a = 11.4334(16) Å, b = 20.243(2) Å, c = 21.805(3) Å, β = 101.113(9)°, V = 4951.9(11) Å3, and Z = 4 for 2]. The structures of 1 and 2 consist of discrete linear [MCr2(ox)6]4− bimetallic trinuclear units, pyridinium cations and crystallization water molecules. The linear trinuclear unit is built from a central trans-diaquametal(II), linked to two Cr(ox)3]3− entities by oxalate bridges. One of the oxalate ions is coordinated to the central metal ion whereas the other two oxalate ligands are non-bridging. In the crystal, intermolecular hydrogen bonds involving oxalate ligands, water molecules and pyridinium cations, build a complex three-dimensional network. Variable-temperature magnetic susceptibility measurements for 1 and 2 indicate a weak ferromagnetic interaction (J = +1.16 and +2.62/+2.70 cm−1 for 1 and 2, respectively) between the two terminal CrIII (SCr = 3/2) and the central high-spin MnII (SMn = 5/2) and CoII (SCo = 3/2) ions. The nature and the amplitude of the exchange interaction are rationalized using DFT calculations and orbital interpretations.

Graphical abstract: Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation

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Article information

DOI
https://doi.org/10.1039/C002468F
Article type
Paper
Submitted
08 Feb 2010
Accepted
07 Apr 2010
First published
26 Apr 2010

Dalton Trans., 2010,39, 4951-4958

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Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation

E. Pardo, C. Train, R. Lescouëzec, K. Boubekeur, E. Ruiz, F. Lloret and M. Verdaguer, Dalton Trans., 2010, 39, 4951 DOI: 10.1039/C002468F

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