In conclusion, we have shed light on the surprising complexity of aliovalent doping in this family of hybrid framework materials. We anticipate that as the investigation of hybrid frameworks advances, the range of defects we have uncovered in thiocyanate frameworks will be reflected in other anion chemistries. These novel defect types will have different energetic formation costs, and the complex orderings will perturb the cooperative properties, such as mechanical flexibility and magnetism. The adaptability of these structures further suggests that guests of significant complexity, including molecular complexes, could be included in these frameworks, whether directly in synthesis or postsynthetically through ion-exchange processes.