The electrical resistivity, crystalline structure and electronic properties calculated from the experimentally measured atomic positions of the compound SmFeAsO$_{0.81}$F$_{0.19}$ have been studied up to pressures ~20GPa. The correlation between the pressure dependence of the superconducting transition temperature (Tc) and crystallographic parameters on the same sample shows clearly that a regular FeAs$_{4}$ tetrahedron maximizes Tc, through optimization of carrier transfer to the FeAs planes as indicated by the evolution of the electronic band structures.