Ba3[LiSbS2(S2)2Cl2]: The first zero-dimensional (OD) lithium metal thioantimonate featuring molecular anions of [LiSbS2(S2)2Cl2]6-

The first lithium metal thioantimonate featuring 0D structure, namely Ba-3[LiSbS2(S-2)(2)Cl-2], has been prepared from a mixture of BaCl2, LiCl, Ba, Sb, and S in an evacuated graphite crucible coated silica tube. The Ba-3[LiSbS2(S-2)(2)Cl-2] crystallizes in space group C2/m (No. 12) with a = 13.308(9) angstrom, b = 12.116(7) angstrom, c = 9.408(6) angstrom, V = 1425.4(16) angstrom(3) and Z = 4. It adopts a new OD structure type with unusual discrete clusters of [LiSbS2(S-2)(2)Cl-2](6-) arranged in a pseudolayer motif extending in ab plane. The Ba2+ cations are located in the interspaces. The molecular anions of [LiSbS2(S-2)(2)Cl-2](6-) can be best regarded as eight-membered rings built of two Li-2(S-2)(2) tetrahedra and two disordered SbS2Cl2 teeter-totter polyhedra via corner-sharing. Another notable structural feature is the occurrence of the LiS2(S-2)(2) tetrahedra which are derived from the LiS 4 tetrahedra by substituting two terminal S2- anions with two disulfide [S-2](2-) units. Disordered SbS2Cl2 teeter-totter polyhedra are derived from the fusing of the two trigonal-pyramidal SbS2Cl units. Moreover, presence of chloride anions in terminal vertexes of SbS2Cl trigonal pyramids as well as Ba-rich ratio may be responsible for ceasing the propagation of Li/Sb/S networks, resulting in the unusual OD structure in the titled compound. In addion, the density functional theory (DFT) study reveals a direct bandgap of 2.6 eV, which can be ascribed to the electronic transitions from the top of valence band dominated by the 3p states of disulfide [S-2](2-) to the 5d states of Ba atoms and 3p states of disulfide [S-2](2-).

Automated summary

A novel lithium metal thioantimonate with a 0D structure has been synthesized, featuring unique discrete clusters in a pseudolayer motif extending in the AB plane. The compound exhibits a direct bandgap of 2.6 eV, attributed to electronic transitions from the valence band dominated by 3p states of disulfide ions to the 5d states of Ba atoms and 3p states of disulfide ions.