BiMn6PO12, A New Bismuth Manganese II/III Oxyphosphate with an Original Manganese–Oxygen Cubic Network

A new bismuth manganese oxyphosphate, BiMn6PO12, with an original cubic structure has been synthesized by solid state reaction from Bi2O3, MnO2, and (NH4)2HPO4 or BiPO4 and Mn3O4 mixtures. Its crystal structure has been determined from single-crystal X-ray diffraction data. It crystallizes in the cubic system with space group Fm m and unit cell parameter a=9.626(1) ?, Z=4. A full-matrix least-squares refinement yielded R=0.044 and Rw=0.045 for 131 independent reflections with I>2sigma(I) collected on a Philips PW100 diffractometer (MoKalpha radiation). The structure of BiMn6PO12 is characterized by a three-dimensional network of manganese–oxygen bonds. The oxygen atoms form a rhombicuboctahedron. The manganese atoms occupy two-thirds of the square faces of this polyhedron and are at the vertices of cuboctahedra. Manganese and oxygen atoms form a Mn12O24 cage, which constitute the strong basic element of the global building. The PO4 tetrahedron is located within this cage and can be moved between two equivalent orientations. The connection between Mn12O24 entities created little cubic holes occupied by bismuth atoms. In this compound all the manganese atoms are crystallographically equivalent and the mean oxidation state of manganese is +2.67. A superstructure, which could be due to PO4 orientations ordering, was evidenced by an electronic diffraction study. BiMn6PO12 exhibits complicated magnetic behavior with several magnetic transitions both in the paramagnetic state and in the low-temperature ordered state.