Die Reaktion des Rhenium(VII)-oxides mit 1,4-Dioxan Re2O6(μ2-OH)2 · 3 C4H8O2 – ein neues Oxidhydroxid mit Metall-(1,4-Dioxan)-Bindung

Reaction of Rhenium(VII) Oxide with 1,4-Dioxane. Re₂O₆(μ₂-OH)₂ · 3 C₄H₈O₂— a Novel Oxide Hydroxide with Metal-(1,4-Dioxane) Bonds The reaction of Re₂O₇ with 1,4-dioxane in the presence of small amounts of H₂O yields the compound Re₂O₆(OH)₂ · 3(1,4-dioxane). It crystallizes in the triclinic space group P¯1 with a = 10.907(3), b = 12.875(4), c = 7.943(2) Å; α = 108.64(2), β = 103.00(2), γ = 102.29(2)°; Z = 2. The complete X-ray structure analysis (R = 2.9? ) shows the crystals to contain dimeric centrosymmetric Re₂O₆(OH)₂-units with two bridging μ₂-OH groups. The ligand spheres around Re are completed towards distorted octahedra by coordinated 1,4-dioxane molecules (one O donor per Re), the latter linking the dimeric units to endless chains. The rest of the 1,4-dioxane molecules are bonded to the OH-groups through hydrogen bridges and have no contact to Re. Mean bond distances are: Re? O(bridge) 2.065 (2.059…2.070(4)) Å, Re? O(1,4-dioxane) 2.478 (2.469 and 2.486(5)) Å, Re? O (terminal) 1.707 (1.694…1.720(5)) Å.