Hybrid inorganic-organic halide materials present many intriguing structural, 1,2 magnetic, electrical, optical, and chemical properties. Perhaps the most transformative applications of these materials have been in photovoltaics and radiation detectors. However, most leading examples employ Pb 2+ -based materials, even though the same Sn 2+ -based materials exist, pose less (but not no) concerns regarding toxicity, and are predicted to provide comparable optoelectronic properties (e.g., band gaps, mobilities). However, a key challenge facing these tin-based materials has been their high carrier concentrations, nominally attributed to the facile oxidation of Sn(II) to Sn(IV). DFT-based calculations of point defects in these materials generally agree that tin vacancies tend to be the largest compensating defect responsible for the large hole concentrations in these materials. Understanding how the material's chemistry influences these defects and their impact on the electronic properties is paramount for further discovery and transformative applications. The nature of the organic cation permits coalescence and ordering of "vacancies" to create perovskite derived structures. Organic ammonium cations, comprising alkylammonium, cyclic alkylammonium, and chiral aromatic molecules, result in the crystallization of a broad diversity of inorganic motifs ranging from zero to three-dimensional inorganic connectivity, with diverse structural motifs within each dimensional category. For example, the layered perovskites (e.g., Ruddlesden-Poppper and Dion-Jacobson type) have been extensively studied for their electronic properties resulting from spatial confinement of the frontier electronics. Compounds with divalent metal halides and alkyldiammonium cations with different carbon lengths tend to produce these layered crystal structures, where the ammonium cations form an electrostatic bridge between different [M X 4 ] 2-layers. However, diammonium heptane, (NH 3 (CH 2 ) 7 NH 3 ) 2+ , appears to behave differently with tin and iodine. When mixed with methylammonium and SnI 2 , it produces a complex, vacancy-ordered, 3D mixed valence material with ordered Sn(IV) sites, (NH 3 (CH 2 ) 7 NH 3 ) 8 (CH 3 NH 3 ) 2 Sn 13 I 46 . Excluding methylammonium appears to also produce a vacancy-ordered compound, (NH 3 (CH 2 ) 7 NH 3 ) 2 Sn 3 I 10 , as depicted in Figure ; however the work was never presented in a peer-reviewed publication. It remains challenging to understand how different organic cations template different structures in these hybrid materials.