We analyze the stability and dynamics of an ion chain confined inside a high-finesse optical resonator. When the dipolar transition of the ions strongly couples to one cavity mode, the mechanical effects of light modify the chain properties close to a structural transition. We focus on the linear chain close to the zigzag instability and show that linear and zigzag arrays are bistable for certain strengths of the laser pumping the cavity. For these regimes the chain is cooled into one of the configurations by cavity-enhanced photon scattering. The excitations of these structures mix photonic and vibrational fluctuations, which can be entangled at steady state. These features are signaled by Fano-like resonances in the spectrum of light at the cavity output.