Chemical bonding analysis and properties of La7Os4C9—A new structure type containing C- and C2-units as Os-coordinating ligands

The new ternary carbide La7Os4C9 was prepared by argon arc-melting of the elements followed by subsequent heat treatment at 900 °C for 250 h. The compound crystallizes monoclinic, in the space group C2/m (a=1198.5(2) pm, b=542.0(1) pm, c=1196.2(2) pm, β=111.04(1)°, V=725.2(2)×106 pm3, Z=2). The structure was determined from single crystal X-ray diffraction data and refined to a residual of R1=0.02 (wR2=0.03) for 4812 unique reflections and 64 variable parameters. Electrical resistivity and magnetic susceptibility measurements characterize the compound as a Pauli-paramagnetic metal. The crystal structure contains bridging C- and terminal C2-units as Os-coordinating ligands, thereby forming polyanions ∞1[Os4(C2)2C5] running along the [101] direction. The polyanions are composed of alternating Os(C2)C2 and OsC3 units with the transition metal in distorted trigonal planar coordination. Charge compensation is ensured by La cations which are situated in-between the polyanions. The carbon–carbon bond (131 pm) within the C2 pairs is slightly shorter than the value of a common C–C double bond, and is discussed on the basis of COHP curves on the one side, and with ELI-D and electron density distributions on the other side. The method of partial ELI-D decomposition is shown to be well suited for the characterization of separated DOS structures in terms of chemical bonding signatures provided by ELI-D. The Os–La interactions are shown to be of a polar multicenter-bonding type with Os playing the role of the electron donor. Compared to an acetylide the C2 species were found to possess a significantly reduced bond order and an enhanced number of electrons in lone pair type spatial regions. This type of species cannot be simply classified in terms of model pictures such as C22− and C24−, respectively.

Graphical AbstractPolar multicenter Os–La bonding in the compound La7Os4C9 is discussed in position space from a combined analysis of the electron localizability indicator (ELI-D) and the electron density. The picture shows five electron density basins (gray translucent) for atom types Os (green spheres) and La (red spheres) and only those parts (in blue colour) of 4 Os–La multicenter ELI-D basins, which are intersected by the electron density basins displayed.Figure optionsDownload as PowerPoint slide