The six-coordinated mononuclear manganese(III) complex [Mn(5-Br-sal-N-1,5,8,12)]ClO4 has been synthesized and isolated in crystalline form. Magnetic measurements and variable-temperature single-crystal X-ray crystallography corroborated with theoretical analysis provided firm evidence for the spin-crossover effects of this system. The monomeric complex cations are made by a hexadentate mixed-donor Schiff base ligand imposing a distorted octahedral geometry and subtle structural effects determining the manifestation of the variable spin properties of the manganese(III) centers. The spin crossover in [Mn(5-Br-sal-N-1,5,8,12)]ClO4 has resulted in an unprecedented crystallographic observation of the coexistence of high-spin (HS; S = 2) and low-spin (LS; S = 1) manganese(III) complex cations in equal proportions around 100 K. At room temperature, the two crystallographically distinct manganese centers are both HS. Only one of the two slightly different units undergoes spin crossover in the temperature range similar to 250-50 K, whereas the other remains in the HS state down to 50 K. The density functional theory calculations, performed as relevant numerical experiments designed to identify the role of orbital and interelectron effects, revealed unedited aspects of the manganese(III) spin-conversion mechanisms, developed in the conceptual frame of ligand-field models.