A rare micro6-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) A, b=20.893(9) A, c=12.301(6) A, and beta=115.853(7) degrees, whereas the polymeric analogue 2 was crystallized in an orthorhombic system, space group P212121, a=13.1941(8) A, b=14.9897(9) A, and c=27.8746(14) A. Variable-temperature magnetic behavior showed the presence of strong antiferromagnetic interaction in both cases.