We observe an inverted crossover resonance in π-driven four-level systems, where F − F = 0, +1. The signal is observed through saturated absorption spectroscopy of the (6s 2 ) 1 S 0 − (6s6p) 3 P 1 transition in 171 Yb, where the nuclear spin I = 1/2. The enhanced absorption signal is used to generate a dispersive curve for 556 nm laser frequency stabilisation and the stabilised light cools 171 Yb atoms in a two-stage magneto-optical trap, achieving temperatures of 20 µK. The Doppler-free spectroscopy scheme is further used to measure isotopic frequency shifts and hyperfine separations for the intercombination line in ytterbium.