Bi3In4S10 and Bi14.7In11.3S38: Two new bismuth sulfides with interesting Bi–Bi bonding

Two new ternary bismuth chalcogenides, Bi3In4S10 and Bi14.7In11.3S38, were synthesized from the reactions of binary sulfides via a two-step flux technique. Single-crystal X-ray diffraction analyses indicate that Bi3In4S10 crystallizes in the non-centrosymmetric space group Pm and Bi14.7In11.3S38 crystallizes in the centrosymmetric space group P21/m. Both compounds adopt three-dimensional frameworks. A distinct structural feature in the two structures is the presence of chains of Bi atoms with alternating short Bi–Bi bonds of around 3.1 Å and longer distances of around 4.6 Å. The optical band gaps of 1.42(2) eV for Bi3In4S10 and 1.45(2) eV for Bi14.7In11.3S38 were deduced from the diffuse reflectance spectra.