Magnetic order in a novel 3D oxalate-based coordination polymer {[Cu(bpy)3][Mn2(C2O4)3]·H2O}n

A heterometallic coordination polymer {[Cu(bpy)3][Mn2(C2O4)3]·H2O}n (1; bpy = 2,2'-bipyridine) was synthesized using a building-block approach and characterized by IR spectroscopy, single-crystal X-ray diffraction, magnetization measurement, and X-band ESR spectroscopy both on a single crystal and a polycrystalline sample. The molecular structure of 1 is made of a three-dimensional (3D) anionic network [Mn2(C2O4)3]n(2n-) and tris-chelated cations [Cu(bpy)3](2+) occupying the vacancies of the framework. In compound 1 magnetic order is confirmed below 12.8 K - magnetization measurements reveal an antiferromagnetic-like network of canted Mn(2+) spins with incorporated paramagnetic Cu(2+) centres. The ESR spectroscopy distinctly shows the phase transition; above T≈ 13 K, single isotropic Lorentzian lines of Mn(2+) ions in the high spin state S = 5/2 were observed, while below this temperature, only characteristic Cu(2+) signals from cations were detected. Thermal decomposition residues of 1 at different temperatures (800-1000 °C) were analyzed by powder X-ray diffraction; by heating the sample up to 1000 °C the spinel oxide CuMn2O4 [94.1(2) wt%] was formed. From the refined structural parameters, it could be seen that the obtained spinel is characterized by the inversion parameter δ∼ 0.8, and therefore the structural formula at room temperature can be written as (tet)[Cu0.17Mn0.83](oct)[Mn1.17Cu0.83]O4.