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The bismuth(III) oxophosphate Bi(PO)O was obtained by hydrothermal synthesis. The unit cell has a = 5.6840(6) Å, b = 7.0334(7) Å, c = 9.1578(9) Å, α = 78.958(2)°, β = 77.858(2)°, γ = 68.992(2)°, V = 331.41(6) Å, space group P1̅, and Z = 2. The crystal chemical formula that reflects the presence of oxo-centered tetrahedra and triangles is [OOBi](PO). The crystal structure contains [OBi]-heteropolyhedral corrugated layers parallel to (001), which alternate along [001] with isolated (PO) tetrahedra. The structural complexity parameters are v = 22 atoms, I = 3.459 bits/atoms, and I = 76.107 bits/unit cell, and thus Bi(PO)O is the simplest pure bismuth(III) oxophosphate.

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