A rare all-Mn decametallic cage from distorted face-sharing cubes

The preparation and crystal structure of a decametallic Mn^II carboxylate cluster containing neutral 2-pyridinealdoxime, (py)C(H)NOH, and its anion, (py)C(H)NO⁻, is reported. The reaction between Mn(O₂CPh)₂ · 2H₂O and (py)C(H)NOH in CH₂Cl₂, in the presence of NH₄PF₆, produces the complex [Mn₁₀(O₂CPh)₁₂{(py)C(H)CNO}₆{(py)C(H)NOH}₂](PF₆)₂ · 2.6CH₂Cl₂ · 1.3H₂O (1 · 2.6CH₂Cl₂ · 1.3H₂O) in good yield. The cationic complex consists of ten Mn^II ions assembled together by four η¹:η¹:η³:μ₄ and two η¹:η¹:η²:μ₃ oximato(−1) ligands, and four η¹:η²:μ₃ ligands to form an unprecedented core, where R = PhCO and R′ = (py)C(H)N. Peripheral ligation is provided by a combination of bridging benzoates and chelating (py)C(H)NOH ligands. Dc magnetic susceptibility studies reveal the presence of dominant antiferromagnetic interactions leading to a spin ground-state of S_T = 0. A survey of the ternary reaction system is attempted with comparisons to previously reported complexes.