Structure, chemical bonding, and 45Sc solid state NMR of Sc2RuSi2

The silicide Sc2RuSi2 was synthesized from the elements by arc-melting. The structure was refined on the basis of single crystal X-ray diffractometer data: Zr2CoSi2 type, C2/m, a = 1004.7 (2), b = 406.8 (1), c = 946.6 (2) pm, β = 117.95 (2), wR2 = 0.0230, 743 F2 values, and 32 variables. The structure consists of a rigid three-dimensional [RuSi2] network in which the two crystallographically independent scandium atoms fill larger cages of coordination numbers 16 and 15, respectively. The [RuSi2] network shows short Ru–Si distances (234–247 pm) and two different Si2 pairs: Si1–Si1 at 247 and Si2–Si2 at 243 pm. Each silicon atom has trigonal prismatic Sc6 (for Si2) or Sc4Ru2 (for Si1) coordination. These building units are condensed via common edges and faces. The various Sc–Sc distances between the prisms range from 327 to 361 pm. From electronic structure investigation within DFT, chemical bonding shows a major role of Ru–Si bonding and the presence of strong electron localization around Si–Si pairs pointing to a polyanionic silicide network [RuSi2]δ−. The 45Sc MAS-NMR spectra recorded at 11.7 and 9.4 T clearly resolve the two distinct scandium sites. The large electric field gradients present at both scandium sites result in typical line shapes arising from second-order quadrupole perturbation effects.