The tessellation of the Euclidean plane by regular polygons has been contemplated since ancient times and presents intriguing aspects embracing mathematics, art, and crystallography. Significant efforts were devoted to engineer specific 2D interfacial tessellations at the molecular level, but periodic patterns with distinct five-vertex motifs remained elusive. Here, we report a direct scanning tunneling microscopy investigation on the cerium-directed assembly of linear polyphenyl molecular linkers with terminal carbonitrile groups on a smooth Ag(111) noble-metal surface. We demonstrate the spontaneous formation of fivefold Ce-ligand coordination motifs, which are planar and flexible, such that vertices connecting simultaneously trigonal and square polygons can be expressed. By tuning the concentration and the stoichiometric ratio of rare-earth metal centers to ligands, a hierarchic assembly with dodecameric units and a surface-confined metal-organic coordination network yielding the semiregular Archimedean snub square tiling could be fabricated.