The Effect of Temperature onto the Crystal Structure of Thioantimonates: Solvothermal Syntheses and Crystal Structures of [Co(dien) 2 ][Co(tren)SbS 4 ] 2 ·0.5H 2 O and {[Co(tren)] 2 [CoSb 2 S 6 ]}·H 2 O

The two new compounds [Co(dien) 2 ][Co(tren)SbS 4 ] 2 ·0.5H 2 O ( 1 ) and {[Co(tren)] 2 [CoSb 2 S 6 ]}·H 2 O ( 2 ) were synthesized applying mixtures of amines as structure directing molecules (dien = diethylenediamine; tren = tris(2‐aminoethyl)amine). Compound 1 represents a pseudo‐polymorph to the compound [Co(dien) 2 ][Co(tren)SbS 4 ] 2 ·4H 2 O. The structure consists of the two complexes [Co(2)(dien) 2 ] 2+ and [Co(1)(tren)SbS 4 ] – with the latter containing a [Sb(V)S 4 ] 3– anion bonded to the Co 2+ cation. The central and new feature of the structure is a heterometallic [CoSb 2 S 6 ] core composed of two [Sb III S 3 ] pyramids and a [CoS 4 ] tetrahedron. The [CoS 4 ] tetrahedron shares two edges with two [Sb III S 3 ] units. The remaining sulfur atom of the [Sb III S 3 ] groups are bonded to two independent [Co(tren)] complexes.