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The structure of a new lithium bis­muth phosphate, LiBi7.37P3O19, consists of infinite OBi4 edge-sharing tetra­hedral chains in the ac plane, which form Bi2O2 layers parallel to the b axis. They are sandwiched between PO4 tetra­hedral and Bi polyhedral layers. The PO4-Bi-PO4 layers are bridged by columns formed by one Bi polyhedron flanked on each side by LiO4 tetra­hedra.
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