Although in the impurity replaces thus forming octahedral units the experimental hyperfine and anisotropic superhyperfine constants and the energies of optical transitions do not fit into the pattern observed for -doped normal perovskite lattices. Seeking to look into this relevant issue first-principles calculations in the framework of the density-functional theory have been carried out for complexes embedded in both and host lattices which display normal and inverted perovskite structures respectively. The present calculations lead to a value of the equilibrium distance, , which is the same for both host lattices within . Despite this fact and in agreement with experimental data the calculated values of both the anisotropic superhyperfine constant, , and the cubic-field splitting parameter, 10Dq, for are found to be higher than those for while Racah parameters are a bit higher for the latter case. All these results, and also the 3% reduction undergone by the hyperfine constant on passing from to are shown to be connected with a parallel increase in the covalency. These surprising results, which cannot be ascribed to a different value, are shown to arise from the internal electric field, , due to all lattice ions lying outside the complex. Although, according to symmetry, is null at site this is shown to be not true in the neighborhood of ligands for the host lattice. The quite different shape of in normal and inverted perovskite lattices is shown to be already understood considering only the first two shells surrounding the complex. The present results demonstrate that the traditional ligand field theory fails to understand the changes undergone by optical and magnetic parameters of a complex when a host lattice is replaced by another one which is not isomorphous. The relevance of present conclusions for understanding the color of -based gemstones is also underlined.