Crystal and electronic structure of a hexacarbonyldiiron cluster tethered to naphthalene‐2‐thiolate ligands

The structure of the previously reported complex bis­(μ-naphthalene-2-thiol­ato-κ2S:S)bis­(tri­carbonyl­iron)(Fe—Fe), [Fe2(C10H7S)2(CO)6], has been characterized by X-ray diffraction. In the solid state, the dinuclear complex adopts a butterfly-like shape, with an equatorial–axial spatial orientation of the naphthalene groups covalently coupled to the [S2Fe2(CO)6] unit. The asym­metric unit contains three independent [(μ-naphthalene-2-thiol­ato)2Fe2(CO)6] mol­ecules. These mol­ecules show inter­molecular π–π stacking inter­actions between the naphthalene rings, which was confirmed by Hirshfield surface analysis. The electronic spectrum of the complex recorded in aceto­nitrile shows a band centered at 350 nm (∊ = 4.6 × 103 M−1 cm−1) and tailing into the visible region. This absorption can be attributed to a π→π* electronic transition within the naphthalene moiety and a metal-based d→d transition.