On the preparation, structure and bonding of ReSCl3

Abstract

The reaction of Re 2 O 7 with a solution of S in S 2 Cl 2 at 100°C produced rhenium sulfur trichloride, ReSCl 3. The compound was found to have a polymeric linear structure [{ReCl 2 (µ µ µ µ-Cl)} 2 (µ µ µ 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 NbCl 4-type and expands the series of similar one-dimensional chain structures. Distorted Re[Cl 4 S 2 ] 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 +3.40 S-1.20 [Cl1-0.68 ] 2 Cl2-0.84 .