Figure 1.

Structural chemistry of helical manganese BPOs. a) Rietveld refinement of high‐resolution X‐ray diffraction of the LiMnBPO, crystallizing in the hexagonal system, P6₅22 (space group 179) with unit cell parameters a = 9.5892(1) Å, c = 15.8525(3) Å, V = 1262.39(3) ų, and Z = 6. b) Representative hexagonal pyramidal single crystal of helical LiMnBPO (Figure S3, Supporting Information). c) Crystal structure of LiMnBPO that is comprised of 1D infinite loop‐branched BPO helices _∞ ¹[BP₂O₈]³⁻ built of alternate BO₄ (blue) and PO₄ (purple) tetrahedra and is further interconnected through MnO₄(OH₂)₂ coordination (green) octahedra. The free threads of helices are occupied by Li cations (yellow spheres), which are in an irregular surrounding of oxygen atoms (Figures S4 and S5, Supporting Information). The crystal water in the structure is shown as red spheres and located within the helical channels. d) HRTEM image depicting the single crystal with sharp reflection displaying its crystallinity in the SAED pattern (inset). e–g) EDX mapping of hexagonal LiMnBPO (Figure S6, Supporting Information) crystals, where a uniform distribution of Mn (orange), P (yellow), and oxygen (red) was achieved confirming the phase‐purity of the product (elements B and Li are beyond the detection limit of the instrument, and therefore, ICP‐AES was conducted).