In this paper we showcase two distinct workflows for materials discovery, one which combines established pertinent experimental techniques and one that incorporates a new computational tool. These enable the isolation and study of two structurally complex materials. We aim to create new structures by combining features of established ones, assisted by the increase in the number of coordination chemistries displayed by the constituent elements. In order to accelerate the investigation of phases at boundaries between known structure types, we combine traditional experimental routes with an iterative algorithmic identification of target compositions based on results from powder X-ray diffraction in order to efficiently target the composition corresponding to the new structure, demonstrating the role of computational analysis beyond high-throughput DFT and AI in the experimental realisation of materials (i.e., in materials discovery). This process was followed by a combination of different diffraction techniques which lead to efficient structure solution.