On the Flexibility of Thioantimonate Networks: Solvothermal Syntheses and Crystal Structures of Six New Thioantimonates(III) with the [Sb4S7]2− Anion

Six new thioantimonates(III) with the Sb₄S₇]^2? anion were obtained under solvothermal conditions with in‐situ formed transition metal complexes as structure directors. In the two isostructural compounds Fe(dien)₂]Sb₄S₇·H₂O ( 1 ) and Co(dien)₂]Sb₄S₇·0.5 H₂O ( 2 ) (dien = diethylenetriamine; space group: P2₁/c) the layered Sb₄S₇]^2? anion is characterized by Sb₈S₈ rings with a diameter of about 9.6·7.6Å. The cation complexes are located above and below the pores of the rings. Despite the larger size of the cation complex the network topology of the third thioantimonate Ni(dien)(tren)]Sb₄S₇ ( 3 ) (tren = tris(2‐aminoethyl)amine; space group: P2₁/n) is similar to that of the first two compounds. In the isostructural thioantimonates M(trien)]Sb₄S₇ (M = Zn ( 4 ); M = Mn ( 5 ); trien = triethylenetetramine; space group: ) the M²⁺ ions are fivefold coordinated by four N atoms of the amine molecule and by one S atom of the thioantimonate anion forming a MN₄S trigonal bipyramid. Sb₈S₁₆ building blocks are the central structural motifs of the anion. Two of the terminal S atoms at the periphery of the Sb₈S₁₆ units are bound to M²⁺ ions and the four remaining terminal S atoms connect adjacent Sb₈S₁₆ groups into the final Sb₄S₇]^2? chain. Ni(tren)]Sb₄S₇ ( 6 ) (space group: ) contains a one‐dimensional anionic chain. The Ni²⁺ ion has two bonds to the Sb₄S₇]^2? anion which is a unique feature in the thioantimonate(III) chemistry. The NiN₄S₂ octahedron is severly distorted with one very long Ni‐S bond of 2.782(2) Å. In all compounds several short S···H distances indicate hydrogen bonding interactions.