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Issue 35, 2010
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Hydrothermal syntheses, crystal structures and physicochemical properties of 2-D and 3-D inorganic coordination cobalt(ii)-sulfitepolymers

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Abstract

The hydrothermal reaction of [CoIII(NH3)6]Cl3 with Na2SO3 yields, depending on the concentration of Na2SO3, compounds {Na[CoII2(SO3)23-OH)(H2O)]} (1) and {Na4[CoII2(SO3)4]} (2). When (NH4)2SO3·H2O was substituted for Na2SO3, the trinuclear mixed valence cobalt(II/III) complex (NH4)4{CoII[CoIII(SO3)3(NH3)3]2}·2H2O (3·2H2O) was isolated. The cobalt-sulfites 1–3·2H2O were structurally characterized. In 1, the 1-D chains along the a-axis of the subunit [CoII(2)CoII(3)(OH)2(SO3)2] are cross-linked with CoII(1) atoms via CoOsulfite and CoOhydroxide bonds in 2-D sheets, that are further stacked through interlayer hydrogen bonds. In 2, the [CoII2(SO3)2] chains along the b-axis are cross-linked with tetrahedral cobalts via CoIIOsulfite bonds in 2-D sheets parallel to the ab-plane and the sheets are further bound to sodium atoms via Na+Osulfite bonds to form a 3-D structure. The 3-D inorganic coordination polymer, 2, crystallizes in the non-centrosymmetric space group P212121. In addition, in compound 2 octahedral and tetrahedral cobalt atoms coexist, which is rather unusual for cobalt clusters. Compound 3·2H2O is a 0-D mixed-valence {[(NH3)3CoIII(μ-SO3)3]CoII[(μ-SO3)3CoIII(NH3)3]}4− trinuclear cluster and can be considered as an octahedral {CoIIO6} complex ligated to two tridentate [(NH3)3CoIII(SO3)3]3− ligands. The trinuclear clusters are stacked through an extended network of hydrogen bonding into a 3-D structure. Variable temperature magnetic susceptibility studies for 1–3·2H2O revealed that 1 and 2 are 2-D magnetic systems with strong antiferromagnetic interaction between the CoII atoms leading to an S = 0 ground state for 1, while in compound 2 there is an almost zero interaction between the cobalt(II) atoms leading to a non-zero ground state. The trinuclear compound 3·2H2O has two diamagnetic CoIII atoms and a high-spin CoII atom with D = 84(1) cm−1, E = 6(1) cm−1 and g = 2.56(1). The IR, the solid-state UV-vis spectra and the thermogravimetric analyses of compounds 1–3·2H2O are also reported.

Graphical abstract: Hydrothermal syntheses, crystal structures and physicochemical properties of 2-D and 3-D inorganic coordination cobalt(ii)-sulfite polymers

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Supplementary files

Article information


Submitted
05 Oct 2009
Accepted
10 Jun 2010
First published
09 Aug 2010

Dalton Trans., 2010,39, 8296-8305
Article type
Paper

Hydrothermal syntheses, crystal structures and physicochemical properties of 2-D and 3-D inorganic coordination cobalt(II)-sulfite polymers

G. I. Chilas, N. Lalioti, T. Vaimakis, M. Kubicki and T. Kabanos, Dalton Trans., 2010, 39, 8296 DOI: 10.1039/B920710D

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