In 1991 the layered organic compound κ-(BEDT-TTF)₂Cu₂(CN)₃ with a triangular lattice was synthesized for the first time. Although originally, the focus was on the superconducting properties under pressure, this frustrated Mott insulator has been the most promising quantum-spin-liquid candidate for almost two decades, widely believed to host gapless spin excitations down to T→0. The recent observation of a spin gap rules out a gapless spin liquid with itinerant spinons and puts severe constraints on the magnetic ground state. This review evaluates magnetic, thermal transport, and structural anomalies around T*= 6 K. The opening of a spin gap yields a rapid drop of spin susceptibility, NMR Knight shift, spin-lattice relaxation rate, and μ-SR spin fluctuation rate, but is often concealed by impurity spins. The concomitant structural transition at T* manifests in thermal expansion, THz phonons and ⁶³Cu NQR relaxation. Based on the field dependence of T*, a critical field of 30–60 T is estimated for the underlying spin-singlet state. Overall, the physical properties are remarkably similar to those of spin-Peierls compounds. Thus, a strong case is made that the ‘6K anomaly’ in κ-(BEDT-TTF)₂Cu₂(CN)₃ is the transition to a valence-bond-solid state and it is suggested that such a scenario is rather the rule than the exception in materials with strong magnetic frustration.