Syntheses, crystal structures, and electronic properties of Ba8Si2US14 and Ba8SiFeUS14

Black single crystals of the new compounds Ba8Si2US14 and Ba8SiFeUS14 have been obtained by high-temperature solid-state methods at 1223 K. These isostructural compounds crystallize in a new structure type in space group C-2h(3) - C2/m of the monoclinic system. The salt-like structure comprises isolated US6 octahedra and MS4 tetrahedra separated by Ba cations. The US6 octahedra form pseudo-layers that are separated by two other pseudo-layers formed by isolated MS4 tetrahedra. These compounds do not show any short S-S interactions. Ba8Si2US14 charge balances with 8 Ba2+, 2 Si4+, 1 U4+, and 14 S2-; Ba8SiFeUS14 can be charge balanced with 8 Ba2+, 1 Si4+, 1 Fe3+, 1 U5+, and 14 S2-. OFT calculations using the HSE functional indicate that the compounds are semiconductors. The calculated band gaps are 1.2 eV and 1.8 eV for Ba8Si2US14 and Ba8SiFeUS14, respectively. (C) 2015 Elsevier Masson SAS. All rights reserved.