Three new thiostannates [Co(C8N5H23)]2Sn2S6 (I), [Fe(C8N5H23)]2Sn2S6 (II) and [Ni(C8N5H23)]2Sn2S6 (III) were synthesized under solvothermal conditions. In all compounds the [Sn2S6]4− anion acts as a bidentate or μ2 ligand bridging two symmetry related [M(C8N5H23)]2+ cations. Despite the identical building units only compounds I and II are isostructural crystallizing in the tetragonal space group I41/a, whereas compound III crystallizes in space group P21/n. A detailed analysis of the intermolecular interactions reveals remarkable differences between I/II and III which may be responsible for the crystallization in different symmetries and space groups. The slightly different bonding situations in the [Sn2S6]4− anion in I/II and III are reflected in the Raman spectra. For all three compounds the UV/Vis spectra show d‐d transitions energetically below the absorption edge.

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The two new thiostannate compounds (trenH) 2 Sn 3 S 7 (1) and {[Mn(tren)] 2 Sn 2 S 6 } (2) (tren = tris-2-aminoethylamine) were obtained under solvothermal conditions. Compound 1 crystallizes in the hexagonal space group P6 3 /mmc with a = 13.2642(19), c = 19.078(3) Å, V = 2906.9(7) Å 3 . The layered [Sn 3 S 7 ] 2− anion is constructed by Sn 3 S 4 semi-cubes sharing common edges. The layers are characterized by large hexagonal pores with dimensions of about 11 × 11 Å 2 . Compound 2 crystallizes in the triclinic space group P1 with lattice parameters a = 7.6485(7), b = 8.1062 (7), c = 12.1805(11) Å, α = 97.367(11), β = 103.995(11), γ = 108.762(10) • , V = 676.17(10) Å 3 . The [Sn 2 S 6 ] 4− anion is composed of two edge-sharing SnS 4 tetrahedra and joins two Mn 2+ -centered complexes by Mn-S bond formation. The Mn 2+ cation is in a trigonal-bipyramidal environment of four N atoms of the tren ligand and one S atom of the thiostannate anion. Both compounds are semiconductors with a band gap of 2.96 eV for 1 and of 2.75 eV for 2.

Six new thioantimonates(III) with the [Sb 4 S 7 ] 2Ϫ anion were obtained under solvothermal conditions with in-situ formed transition metal complexes as structure directors. In the two isostructural compounds [Fe(dien) 2 ]Sb 4 S 7 · H 2 O (1) and [Co(dien) 2 ]Sb 4 S 7 · 0.5 H 2 O (2) (dien ϭ diethylenetriamine; space group: P2 1 /c) the layered [Sb 4 S 7 ] 2Ϫ anion is characterized by Sb 8 S 8 rings with a diameter of about 9.6 · 7.6 Å . 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)]Sb 4 S 7 (3) (tren ϭ tris(2-aminoethyl-)amine; space group: P2 1 /n) is similar to that of the first two compounds. In the isostructural thioantimonates [M(trien)]Sb 4 S 7 (M ϭ Zn (4); M ϭ Mn (5); trien ϭ triethylenetetramine; space group: P1) the M 2ϩ ions are fivefold coordinated by four N atoms of the amine 1687 molecule and by one S atom of the thioantimonate anion forming a MN 4 S trigonal bipyramid. Sb 8 S 16 building blocks are the central structural motifs of the anion. Two of the terminal S atoms at the periphery of the Sb 8 S 16 units are bound to M 2ϩ ions and the four remaining terminal S atoms connect adjacent Sb 8 S 16 groups into the final [Sb 4 S 7 ] 2Ϫ chain. [Ni(tren)]Sb 4 S 7 (6) (space group: P1) contains a one-dimensional anionic chain. The Ni 2ϩ ion has two bonds to the [Sb 4 S 7 ] 2Ϫ anion which is a unique feature in the thioantimonate(III) chemistry. The NiN 4 S 2 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.

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