Calcite is a ubiquitous mineral in nature. Heavy alkaline-earth elements with large ionic radii such as Sr²⁺ and Ba²⁺ are highly incompatible to calcite. Our previous study clarified that incompatible Sr²⁺ ions can be structurally incorporated into calcite through crystallization from amorphous calcium carbonate (ACC). In this study, we synthesized Sr-doped calcite with Sr/(Sr + Ca) up to 30.7 ± 0.6 mol% and Ba-doped calcite with Ba/(Ba + Ca) up to 68.6 ± 1.8 mol%. The obtained Ba-doped calcite samples with Ba concentration higher than Ca can be interpreted as Ca-containing barium carbonates with the calcite structure which have not existed so far because barium carbonate takes the aragonite structure. X-ray diffraction (XRD) patterns of the Sr-doped and Ba-doped calcite samples obtained at room temperature showed that reflection 113 gradually weakened with increasing Sr/(Sr + Ca) or Ba/(Ba + Ca) ratios. The reflection 113 disappeared at Ba/(Ba + Ca) higher than 26.8 ± 1.6 mol%. Extinction of reflection 113 was reported for pure calcite at temperatures higher than 1240 K, which was attributed to the rotational (dynamic) disorder of CO₃²⁻ in calcite. Our Molecular Dynamics (MD) simulation on Ba-doped calcite clarified that the CO₃²⁻ ions in Ba-doped calcites are in the static disorder at room temperature. The CO₃²⁻ ions are notable tilted and displaced from the equilibrium position of pure calcite.