Heteroanionic materials show promising potential as 2D semiconductors due to their tunable band gaps, making them excellent candidates for photocatalytic water splitting applications. We conducted detailed theoretical and experimental analysis of two selected materials by synthesizing crystals through chemical vapor transport and investigating the impact of anion variation on crystal structure and properties. Using powder X-ray diffraction and convergent beam electron diffraction, we elucidated the non-centrosymmetric space groups of these compounds. Thermochemical studies revealed the influence of the crystal structure on the decomposition points of both compounds. Theoretical investigations predict that both materials are indirect bandgap semiconductors, which is confirmed by electron energy loss spectroscopy and photoluminescence studies.