Abstract
The crystal structure of the new iodobismuthate (PyPy)2(PyPyH)2Bi6I26 was found to consist of unusual hexanuclear [Bi6I26]6− anions containing the linear I42− unit, and the experimental Bi–I bond lengths in this anion were used to obtain the relationship between bond length and bond energy. A statistical analysis of 229 crystal structures of iodobismuthates, based on the quantum chemically estimated strength of Bi–I bonds, revealed that the total energy of the Bi3+ polyhedron remains virtually constant at 64 ± 2 kcal mol−1, regardless of its geometry within this family of materials. Thus, the polyhedron geometry flexibly adapts to the relatively weak interactions between iodobismuthate anions and embedded cations.
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