Lithiotantite, ideally LiTa3O8

Lithiotantite (lithium tritantalum octaoxide) and lithiowodginite are natural dimorphs of LiTa3O8, corresponding to the laboratory-synthesized L-LiTa3O8 (low-temperature form) and M-LiTa3O8 (intermediate-temperature form) phases, respectively. Based on single-crystal X-ray diffraction data, this study presents the first structure determination of lithiotantite from a new locality, the Murundu mine, Jenipapo District, Itinga, Minas Gerais, Brazil. Lithiotantite is isotypic with LiNb3O8 and its structure is composed of a slightly distorted hexagonal close-packed array of O atoms stacked in the [-101] direction, with the metal atoms occupying half of the octahedral sites. There are four symmetrically non-equivalent cation sites, with three of them occupied mainly by (Ta5+ + Nb5+) and one by Li+. The four distinct octahedra share edges, forming two types of zigzag chains (A and B) extending along the b axis. The A chains are built exclusively of (Ta,Nb)O6 octahedra (M1 and M2), whereas the B chains consist of alternating (Ta,Nb)O6 and LiO6 octahedra (M3 and M4, respectively). The average M1—O, M2—O, M3—O and M4—O bond lengths are 2.011, 2.004, 1.984, and 2.188 Å, respectively. Among the four octahedra, M3 is the least distorted and M4 the most. The refined Ta contents at the M1, M2 and M3 sites are 0.641 (2), 0.665 (2), and 0.874 (2), respectively, indicating a strong preference of Ta5+ for M3 in the B chain. The refined composition of the crystal investigated is Li0.96Mn0.03Na0.01Nb0.82Ta2.18O8.