The two novel compounds, [Mn(tren)]Sb2S4 (1 and 2), were obtained by the reaction of elemental Mn, Sb, and S in aqueous solutions of tren (tren = tris(2-aminoethyl)amine, C6H18N4) after different reaction times. Compound 1 is formed up to a reaction time of 13 d, and an extension of the reaction time leads to the formation of 2. Both compounds crystallize in monoclinic space groups (1, P2(1)/c; 2, C2/c). In 1, the two unique SbS3 trigonal pyramids share a common S atom to form a Sb2S5 unit. Two S atoms of this group have a bond to Mn2+ yielding a MnSb2S3 heteroring in the boat conformation. The Sb2S5 moieties are joined via common corners into the final undulated [Sb2S4]2- anion which is directed along [001]. The structure of 2 contains the [Mn(tren)]2+ ion, one SbS3 pyramid, and a SbS4 unit. Two symmetry-related SbS4 groups share an edge, forming a Sb2S6 group containing a Sb2S2 ring. This group is joined via corners to two SbS3 pyramids on both sides producing a Sb4S4 ring. The Sb2S2 and Sb4S4 rings are condensed into the final [Sb2S4]2- anion which runs along [010]. The [Mn(tren)] groups are bound to the thioantimonate(III) backbone on opposite sides of the Sb4S4 ring, and a small MnSbS2 ring is formed. In both structures, weak S...H bonds are found which may contribute to the stability of the materials. The two compounds decompose in one step upon heating, and only MnS and Sb2S3 could be identified as the crystalline part of the decomposition products. Both compounds can also be prepared under solvothermal conditions using MnSb2S4 as starting material. Compounds 1 and 2 are obtained from this ternary material in a high yield.

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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The new charge neutral complex [Cr(tren)SbS3]·H2O was synthesized under solvothermal conditions applying CrCl3·6H2O, Sb2S3, and S as starting material in an aqueous tren solution (tren = tris(2‐aminoethyl)amine)). The compound crystallizes in the non‐centrosymmetric space group P212121 with a = 8.7779(15), b = 10.7122(17), c = 15.4286(18) Å, V = 1450.8(4) Å3. In the structure the Cr3+ ion is surrounded by four N atoms of the amine molecules and by two S atoms of a trigonal pyramidal [SbS3]3− group, i.e., the latter acts as a bidentate ligand. A three‐dimensional network is formed via hydrogen bonds between the complexes and water molecules. The main resonances in the Raman spectrum can be explained on the basis of calculated data. The most intense band is due to the Sb‐S stretching vibration. The thermal properties were investigated by DTA‐TG measurements. On heating [Cr(tren)SbS3]·H2O decomposes in two distinct steps. The first step corresponds to the removal of the water molecules and the second step to the loss of the tren ligand.