The title compounds 1, 2, and 3 were synthesized through the conventional heating and solvothermal synthesis. As reported in the literature, we found that small organic ligand based Bi complexes can be readily synthesized through solvothermal synthesis, however, the stereochemical activity of the bismuth center lead to the formation of phase impure products (Figure and S19) which further poses challenges to obtain phase pure products. On the other hand, conventional heating and stirring proved to be successful in order to harness phase pure bioctahedral bismuth complexes. Therefore, we decided to synthesize the complexes through two methods and the solvothermal method proved more successful in yielding crystals of the complexes of sufficient quality for structural determination, which has been proven in the past to be rather challenging. However, we observed that the cooling process during the solvothermal synthesis was the key step in controlling the quality of the single crystals obtained from this method. A quick cooling of the reaction mixture from 150 C to 35 C in ACN in 6 hours led to the formation of small poor-quality crystals, unsuitable for diffraction. In contrast, when the cooling process was undertaken over 5 days, sizeable crystals, suitable for single crystal X-ray diffraction (SCXRD), were obtained. Additionally, we also managed to grow the single crystals for complexes 1 and 3 through the conventional methods of slow solvent evaporation, solvent diffusion and vapor diffusion while for complex 2, we failed to prepare the crystals for the SCXRD through the conventional methods.