Inorganic Chemistry, Vol.53, No.11, 5674-5683, 2014
Synthesis, Crystal Structure, and Magnetic Characterization of the Three-Dimensional Compound [Co-2(cbut)(H2O)(3)](n), (H(4)cbut=1,2,3,4-Cyclobutanetetracarboxylic Acid)
A novel cobalt(II) complex of formula [Co-2(cbut)(H2O)(3)](n) (1) (H(4)cbut = 1,2,3,4-cyclobutanetetracarboxylic acid) has been synthesized under hydrothermal conditions and its crystal structure has been determined by means of synchrotron radiation and neutron powder diffraction. The crystal structure of 1 consists of layers of cobalt(II) ions extending in the bc-plane which are pillared along the crystallographic a-axis through the skeleton of the cbut(4-) ligand. Three crystallographically independent cobalt(II) ions [Co(1), Co(2), and Co(3)] occur in 1. They are all six-coordinate with four carboxylate-oxygens [Co(1)-Co(3)] and two cis-[Co(1)] or trans-water molecules [Co(2) and Co(3)] building distorted octahedral surroundings. Regular alternating double oxo(carboxylate) [between Co(1) and Co(la)] and oxo(carboxylate) plus one aqua and a syn-syn carboxylate bridges [between Co(1) and Co(2)] occur along the crystallographic b-axis, the values of the cobalt-cobalt separation being 3.1259(8) and 3.1555(6) angstrom, respectively. These chains are connected to the Co(3) atoms through the OCO carboxylate along the [0 (1) over bar1] direction leading to the organic-inorganic bc-layers with Co(1)-OCO(anti-syn)-Co(3) and Co(2)-OCo(anti-anti)-Co(3) distances of 5.750(2) and 4.872(1) angstrom. The shortest interlayer cobalt-cobalt separation through the cbut(4-) skeleton along the crystallographic a-axis is 7.028(2) angstrom. Variable-temperature magnetic susceptibility measurements show the occurrence of antiferromagnetic ordering with a Neel temperature of 5.0 K, followed by a field-induced ferromagnetic transition under applied dc fields larger than 1500 Oe. The magnetic structure of 1 has been elucidated at low temperatures in zero field by neutron powder diffraction measurements and was found to be formed by ferromagnetic chains running along the b-axis which are antiferromagnetically coupled with the Co(3) ions through the c-axis giving rise to noncompensated magnetic moments within each bc-layer (ferrimagnetic plane). The occurrence of an antitranslation operation between these layers produces a weak interlayer antiferromagnetic coupling along the a-axis which is overcome by dc fields greater than 1500 Oe resulting in a phase transition toward a ferromagnetic state (metamagnetic behavior).