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Issue 6, 2008
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Supramolecular motifs and solvatomorphism within the compounds [M(bpy)3]2[NbO(C2O4)3]Cl·nH2O (M = Fe2+, Co2+, Ni2+, Cu2+ and Zn2+; n = 11, 12). Syntheses, structures and magnetic properties

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Abstract

Solvatomorphism has been found between two series of complexes of the composition [M(bpy)3]2[NbO(C2O4)3]Cl·nH2O [M = Fe2+ (1, 2), Co2+ (3, 4), Ni2+ (5, 6), Cu2+ (7) and Zn2+ (8, 9); bpy = 2,2′-bipyridine)], crystallizing in the monoclinic space groupP21/c [3, 5, 8 (n = 11)] or in the orthorhombic space groupP212121 [2, 4, 6, 7 (n = 12)]. All the structures contain two symmetry independent [M(bpy)3]2+ cations, one [NbO(C2O4)3]3− anion, one Cl anion, and crystal water molecules. The cations possess a trigonally distorted octahedral geometry, with an additional tetragonal distortion in 7. Analysis of crystal packing reveals a specific type of supramolecular contact comprising four bipyridine ligands from two neighbouring [M(bpy)3]2+ cations—quadruple aryl embrace (QAE) contact. The contact is realized by the alignment of two molecular two-fold rotation axes, preserving the parallel orientation of the molecular three-fold rotation axes. The resulting two-dimensional honeycomb lattices of [M(bpy)3]2+ cations are placed between the hydrogen bonding layers made of [NbO(C2O4)3]3− and Cl anions and the majority of the crystal water molecules. The temperature-dependent magnetic susceptibility measurements (1.8–300 K) show a significant orbital angular momentum contribution for 3 and 4 (high-spin Co2+), the influence of zero-field splitting for 5 and 6 (Ni2+) and a substantially paramagnetic Curie behaviour for the Cu2+ compound (7).

Graphical abstract: Supramolecular motifs and solvatomorphism within the compounds [M(bpy)3]2[NbO(C2O4)3]Cl·nH2O (M = Fe2+, Co2+, Ni2+, Cu2+ and Zn2+; n = 11, 12). Syntheses, structures and magnetic properties

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Article information


Submitted
24 May 2007
Accepted
23 Oct 2007
First published
26 Nov 2007

Dalton Trans., 2008, 742-754
Article type
Paper

Supramolecular motifs and solvatomorphism within the compounds [M(bpy)3]2[NbO(C2O4)3]Cl·nH2O (M = Fe2+, Co2+, Ni2+, Cu2+ and Zn2+; n = 11, 12). Syntheses, structures and magnetic properties

M. Jurić, B. Perić, N. Brničević, P. Planinić, D. Pajić, K. Zadro, G. Giester and B. Kaitner, Dalton Trans., 2008, 742
DOI: 10.1039/B707937K

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