Metastable Bi₈Ni₈S by Reductive Pseudomorphosis of Bi₈Ni₈SI₂

The bimetallic subsulfide Bi₈Ni₈S was synthesized by reduction of Bi₈Ni₈SI₂ with n-BuLi. Bi₈Ni₈S is metastable and decomposes exothermically at about 180°C. In a pseudomorphosis, the shiny black crystals of the precursor were preserved, while the iodide ions were extracted and the pre-formed ¹ _\infinity[Bi₈Ni₈S] fragments rearranged into a pseudo-hexagonal rod packing [space group Pbam, a = 1750.14(7) pm, b = 1007.7(2) pm, c = 419.6(3) pm]. The rods have an effective diameter of about 1 nm and consist of an outer octagonal tube of bismuth atoms and an inner octagonal tube of nickel atoms. This arrangement markedly resembles the columnar Ta₄Te₄Si structure type. The difference comes with the disulfide groups that reside on the cen-tral axis. Interatomic distances inside the rods are almost not affected by the reduction, and thus the electronic band structure is not much altered. Yet, the additional electrons raise the Fermi level into a local maximum of the density of states and occupy predominantly antibonding Ni–Ni and S–S states. The dominant Bi–Ni multicenter bonding is accompanied by localized two-center bonds between nickel atoms. The charges of the nickel atoms as well as ELI-D basin populations of Ni– Ni and Ni–Bi bonds change considerably, indicating that the tube is (un)charging quite flexibly and acts as an electron reservoir. In contrast to the iodide precursor, the weak Pauli paramagnetism of Bi₈Ni₈S is slightly enhanced and spin correlations are observed below 20 K.