Tetravalent ruthenium porphyrin, 2

The crystal structure of μ-oxo-bis[(octaethylporphinato)ruthenium(IV) chloride] benzene solvate, [Ru(IV)-(oep)Cl]2O-C6H6, was determined by the X-ray method. The complex crystallizes in the tetragonal space group P4/nnc, a = 13.912(2) A, c = 17.821(4) A, and Z = 2. The structure was solved by the heavy-atom method and refined to R = 0.084 for 958 reflections. The [Ru(IV)(oep)Cl]2O complex has the crystallographic D4-422 symmetry and contains the binuclear (Cl)N4Ru-O-RuN4(Cl) coordination group with the Ru-O(μ) distance of 1.793(2) A, the Ru-Cl distance of 2.320(6) A, and the Ru-N distance of 2.038(9) A. The Ru-O-Ru bond is explicitly linear, and the two porphinato cores rotate around the Ru-O-Ru bond by 21.00 from the eclipsed form. The porphinato core is planar within 0.04 A, and the Ru atom is displaced only by 0.07 A out of the plane defined by the four porphinato nitrogen atoms toward the bridging O atom. These results are compared with those of the previously reported [Ru(IV)(oep)(OH)2]O-CH3OH crystal. (author)