Not yet reviewed by Pith; the record is open.

Photo-excited quantum materials can be driven into thermally inaccessible metastable states that exhibit structural, charge, spin, topological and superconducting orders. Metastable states typically emerge on timescales set by the intrinsic electronic and phononic energy scales, ranging from femtoseconds to picoseconds, and can persist for weeks. Therefore, studies have primarily focused on ultrafast or quasi-static limits, leaving the intermediate time window less explored. Here we reveal a metastable state with broken glide-plane symmetry in photo-doped Ca$_2$RuO$_4$ using time-resolved optical second-harmonic generation and birefringence measurements. We find that the metastable state appears long after intralayer antiferromagnetic order has melted and photo-carriers have recombined. Its properties are distinct from all known states in the equilibrium phase diagram and are consistent with intralayer ferromagnetic order. Furthermore, model Hamiltonian calculations reveal that a non-thermal trajectory to this state can be accessed via photo-doping. Our results expand the search space for out-of-equilibrium electronic matter to metastable states emerging at intermediate timescales.