Chromous carbonates containing a square-grid layer of {Cr₂(CO₃)₄}⁴ based on a dichromium(II,II) paddlewheel core

Polymeric coordination compounds based on Cr2n+ paddle-wheel building blocks with non-carboxylate O,O-donor ligands chelating and bridging the Cr-Cr centers have been underexplored hitherto. This paper reports the synthesis and crystal structure of a new homo-valent chromium(ii,ii) compound, Na3HCr2(CO3)4·10H2O (1). It has a two-dimensional structure in which the paddlewheel chromium(ii,ii) units of Cr2(CO3)44- are cross-linked through the carbonate groups. The layers are stacked along the [100] direction, and Na ions fill the intra and interlayer spaces with a neighboring layer distance of about 11.3 Å. The investigation of the primary magnetic properties and theoretical studies with density functional theory (DFT) reveal the partial paramagnetic properties of compound 1 arising from the Boltzmann distribution between a ground state σ2π4δ2 with S = 0 and a low-lying excited state σ2π4δδ* with S = 1 for the Cr2(ii,ii) dimer. According to Raman spectra measurements combined with theoretical calculations, the two Raman bands in the small-wavenumber region at 335 and 297 cm-1 were assigned to the vibration of the Cr-O bonds and the band at 371 cm-1 was assigned to the stretching of the Cr-Cr quadruple bond.