A Coordination Polymer based on Interconnection of Thioantimonate(III) and [Mn(terpy)]2+ Complexes: Synthesis, Crystal Structure, and Properties of {[(Mn(terpy))2Sb4S8]·0.5H2O}n.

Applying Schlippe's salt, Na3SbS4·9H2O, in the presence of the in‐situ formed [Mn(terpy)]2+ complex (terpy = 2,2':6',2''‐terpyridine) the new compound {[(Mn(terpy))2Sb4S8]·0.5H2O}n (I) could be obtained under solvothermal conditions. Interestingly, in the crystal structure the two unique Mn2+ cations adopt different environments to form a MnN3S3 octahedron and a MnN3S2 trigonal pyramid. The trigonal pyramidal SbS33– anions share common edges yielding a Sb8S8 ring. Covalent bonds between Mn2+ and S2– generate MnSb2S3 and Mn2Sb4S6 heterocycles. The Sb8S8 and Mn2Sb4S6 rings are condensed to form a chain. The MnN3S3 octahedron and the MnN3S2 polyhedron share a common S2– anion and antiferromagnetic properties are observed mediated by superexchange interactions. {[(Mn(terpy))2Sb4S8]·0.5H2O}n shows luminescence in the blue‐green spectral range, assigned to combined contributions from Mn2+ ions and from the organic ligand. [ABSTRACT FROM AUTHOR]