On the preparation, structure and bonding of ReSCl₃

Chem. Met. Alloys 8 (2015) 43-54

https://doi.org/10.30970/cma8.0306

S.V. VOLKOV, V.V. SUBBOTIN, P.Yu. DEMCHENKO, R.E. GLADYSHEVSKII, O.G. YANKO, L.B. KHARKOVA

The reaction of Re₂O₇ with a solution of S in S₂Cl₂ at 100°C produced rhenium sulfur trichloride, ReSCl₃. The compound was found to have a polymeric linear structure [{ReCl₂(μ-Cl)}₂(μ-S)₂]_∞, which represents a new structure type (space group C2/m, a = 11.4950(7), b = 6.5626(3), c = 5.9938(4) Å, β = 95.199(4)°, Z = 4). The structure is closely related to the NbCl₄-type and expands the series of similar one-dimensional chain structures. Distorted Re[Cl₄S₂] octahedra share edges to form infinite straight chains along the [010] direction and the Re atoms are arranged in pairs with alternatively short (2.965 Å) and long (3.598 Å) Re–Re distances. Electronic structure calculations and chemical bonding analysis, using the electron density/electron-localizability indicator (ELI) approach, indicated overall metallic character and revealed a combination of covalent polar Re–Cl and Re–S bonds and weak Re–Re non-polar metallic bonds, yielding the ELI-based oxidation numbers (ELIBON) Re^+3.40S^–1.20[Cl1^–0.68]₂Cl2^–0.84.

The reaction of Re₂O₇ with a solution of S in S₂Cl₂ at 100°C gave ReSCl₃, a polymer exhibiting an one-dimensional chain structure [{ReCl₂(μ-Cl)}₂(μ-S)₂]_∞, with covalent polar Re–Cl, Re–S bonds and weak Re–Re non-polar metallic bonds.

Keywords

Rhenium sulfidochlorides / Crystal structure / One-dimensional chain structures / Density functional calculations / Electron localizability indicator / Chemical bonding