The fine structure of the transitions in the (X, υ″ = 0 → (B, c), υ′ = 2) band system in K85Rb is studied by using selective Doppler-free spectroscopy techniques. Energy shifts of the perturbed levels due to spin-spin, spin-rotation and spin-orbit interactions were analyzed and modeled within the effective Hamiltonian approach. Molecular and coupling constants were determined, which successfully model the experimental observations.