The need to control metal distances received further impetus with the advent of single atom catalysis (SAC), where substantial performance improvements could be attributed to metal centers in certain distance ranges . MOFs offer a strategic advantage in that both the primary coordination environment and the spacing of metal sites is precisely determined by the crystalline lattice. Isoreticular expansion of MOF frameworks furthermore offers the ability to increase the metal distance along with the pore size and surface area . But to exploit the power of positional isomerism for extended materials, precision access to a suite of compositionally identical, 20 isostructural compounds, which differ only in the distribution of atoms over well-defined sites is required. Here we show a synthetic approach that grants access to "structomers" of extended materials, which can serve to fulfill the need for location optimization that is met by positional isomers in molecular chemistry (Fig. ).