Synthesis of a Mn₆ Cluster and Its Self-Assembly of an Azido-Bridged Polymer^†

A rare μ₆-oxo-centered Mn₆ mixed-valent cluster (1) is prepared and used as a secondary building unit for the self-assembly of its azido-bridged polymeric analogue (2) in a systematic way with the retention of the Mn₆ core of 1. Both complexes are characterized by X-ray single-crystal structure determination. The complex 1 was crystallized in a monoclinic system, space group P2₁, a = 11.252(5) Å, b = 20.893(9) Å, c = 12.301(6) Å, and β = 115.853(7)°, whereas the polymeric analogue 2 was crystallized in an orthorhombic system, space group P2₁2₁2₁, a = 13.1941(8) Å, b = 14.9897(9) Å, and c = 27.8746(14) Å. Variable-temperature magnetic behavior showed the presence of strong antiferromagnetic interaction in both cases.