Iron(III), chromium(III) and cobalt(II) complexes with squarate: Synthesis, crystal structure and magnetic properties

The preparation and variable temperature-magnetic investigation of three squarate-containing complexes of formula [Fe-2(OH)(2)(C4O4)(2)(H2O)(4)]center dot 2H(2)O (1) [Cr-2(OH)(2)(C(4)O4)(2)(H2O)(4)]center dot 2H(2)O (2) and [Co(C4O4)(H2O)(4)](n) (3) [H2C4O4 = 3.4-dihydroxycyclobutene-1,2-dione (squaric acid)] together with the crystal structures of 1 and 3 are reported. Complex 1 contains discrete centrosymmetric [Fe2(OH) 2( C4O4)(2)(H2O)(4)] diiron(II) units where the iron pairs are joined by a di-mu-hydroxo bridge and two squarate ligands acting as bridging groups through adjacent oxygen atoms. Two coordinated water molecules in cis position complete the octahedral environment at each iron atom in 1. The iron-iron distance with the dinuclear unit is 3.0722(6) angstrom and the angle at the hydroxo bridge is 99.99(7)degrees, values which compare well with the corresponding ones in the isostructural compound 2 (2.998 angstrom and 99.47 degrees) whose structure was reported previously. The crystal structure of 3 contains neutral chains of squarato-O-1, O-3-bridged cobalt(II) ions where four coordinated water molecules complete the six-coordination at each cobalt atom. The cobalt-cobalt separation across the squarate bridge is 8.0595(4) angstrom. A relatively important intramolecular antiferromagnetic coupling occurs in 1 whereas it is very weak in 2, the exchange pathway being the same [J = -14.4 (1) and -0.07 cm(-1) (2), the spin Hamiltonian being defined as (H) over cap - -J (S) over cap (1)center dot(S) over cap (2)]. A weak intrachain antiferromagnetic interaction between the high-spin cobalt(II) ions occurs in 3 (J = -0.30 cm(-1)). The magnitude and nature of these magnetic interactions are discussed in the light of their respective structures and they are compared with those reported for related systems. (C) 2011 Elsevier B. V. All rights reserved.