Synthesis and structures of Sc₇Cl₁₂ and Zr₆Cl₁₅

The indicated nine‐electron clusters of scandium and zirconium are formed in transport reactions at 880/900°C and 750/600°C, respectively. Sc₇Cl₁₂ (R¯3, a – 12.959(2), c – 8.825(2), Z – 3) can be described as c.c.p. Sc₆Cl₁₂ clusters with isolated metal atoms in all octahedral interstices or as Sc³⁺(Sc₆Cl₆ⁱCl₆^i−a) ³⁻ with Sc³⁺ in Clⁱ octahedra between Sc₆Cl 123− sheets. Metal‐metal distances within the cluster are 3.201−3.230(2) Å. Zr₆Cl₁₂ⁱCl 6/3a crystallizes in the Ta₆Cl₁₅ structure (Ia3d, a – 21.141(3) Å, Z – 16) with d(ZrZr) = 3,199–3.214(4) Å. Apparent residual electron density is found in the center of both clusters, amounting to Z∼7.6 (Sc) and ∼6 (Zr) based of refinement of oxygen in these positions. The effect is thought to probably arise from errors in the diffraction data rather than partial incorporation of light nonmetal atoms such as oxygen or fluorine. Observed metal‐metal distances are compared with those in other clusters.