Abstract: | The solid‐state‐melt reaction of (NH4)2Re2F8] · 2H2O with 2‐hydroxypyridine (2‐HOpy) produced dark‐red Re2(2‐Opy)4F2 ( 1 ). This air‐stable compound was obtained in crystalline form as 1· CHCl3. It was characterized in the solid state by single‐crystal X‐ray diffraction and in solution by UV/Vis spectroscopy and cyclic voltammetry. 1· CHCl3 forms triclinic crystals with α = 8.3254(5) Å, b = 8.5563(5) Å, c = 11.6784(8) Å, α = 82.723(3)°, β = 75.769(3) °, γ = 64.407(2) °. The Re–Re and Re–F distances were 2.2091(7) and 2.115(6) Å, respectively. The molecule is isostructural with the corresponding chloro derivative. |