A Coordination Polymer based on Interconnection of Thioantimonate(III) and [Mn(terpy)] 2+ Complexes: Synthesis, Crystal Structure, and Properties of {[(Mn(terpy)) 2 Sb 4 S 8 ]·0.5H 2 O} n

Applying Schlippe's salt, Na 3 SbS 4 · 9H 2 O, in the presence of the in‐situ formed [Mn(terpy)] 2+ complex (terpy = 2,2':6',2''‐terpyridine) the new compound {[(Mn(terpy)) 2 Sb 4 S 8 ] · 0.5H 2 O} n ( I ) could be obtained under solvothermal conditions. Interestingly, in the crystal structure the two unique Mn 2+ cations adopt different environments to form a MnN 3 S 3 octahedron and a MnN 3 S 2 trigonal pyramid. The trigonal pyramidal SbS 3 3– anions share common edges yielding a Sb 8 S 8 ring. Covalent bonds between Mn 2+ and S 2– generate MnSb 2 S 3 and Mn 2 Sb 4 S 6 heterocycles. The Sb 8 S 8 and Mn 2 Sb 4 S 6 rings are condensed to form a chain. The MnN 3 S 3 octahedron and the MnN 3 S 2 polyhedron share a common S 2– anion and antiferromagnetic properties are observed mediated by superexchange interactions. {[(Mn(terpy)) 2 Sb 4 S 8 ] · 0.5H 2 O} n shows luminescence in the blue‐green spectral range, assigned to combined contributions from Mn 2+ ions and from the organic ligand.