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Inorganic-organic hybrid halogen bithmutates have attracted much attention due to the huge structural diversity and promising physical properties1: photochemical and photophysical properties, ferroelectricity, and others. Bismuth(III) forms quite a number of halide complexes with various cations. The halobithmutate’s anions assembling occurs as a result of {BiX6} octahedral sharing by vertex, edges or faces, resulting in polynuclear anions involving from 2 to 10 octahedra or coordination polymers. In cases where X = I or Br, the anionic substructure may be completed with X2, X-, Xn- moieties. The physical properties of the resulting hybrid compounds are associated both with the dimension of the anion, the nature of the cation, and the strength and number of weak interactions between them: N-H···I, O-H···I, I···I. However, an unambiguous relationship between the structure of selected organic cations, the synthesis conditions and the structure of formed halogen bithmutates not yet been identified. Herein we report on the crystal structure and synthesis of iodobismuthates of different adamantane’s derivations: azomethines and amino-. We present the possibility of formation different iodobismuthates for the same cation, depending on the synthesis conditions and the ratio of the Bi:cation. We would draw your attention to the comparable system of the weak interactions for the same cations in the iodobismuthates, and also some cation’s iodides.