Mertieite-II, Pd8Sb2.5As0.5, crystal-structure refinement and formula revision

Abstract

ABSTRACTThe crystal structure of the mineral mertieite-II from the Kaarreoja River, Inari commune, Finnish Lapland, Finland, was refined to R1 = 0.0222 (I) and 0.0228 (II) on the basis of X-ray diffraction data collected from two single crystals. The mineral is trigonal, space group is $R\bar 3c$. The unit-cell parameters for the two crystals are determined as: a = 7.5172(3), c = 43.037(2) Å, V = 2106.1(2) Å3 (I); a = 7.5135(4), c = 43.003(3) Å, V = 2102.4(3) Å3 (II) with Z = 12. The occupancies of the Sb and As position in the structure were refined according to the Sb:As ratio of each crystal. The position As1 (Wyckoff 6b) is completely filled by As atoms. Any excess of As is distributed together with Sb on structural position M1 (Wyckoff 12c). The crystal chemical formulae are defined as Pd8Sb1.5(Sb0.94As0.06)As0.5 (crystal I) and Pd8Sb1.5(Sb0.88As0.12)As0.5 (crystal II). As → Sb substitution of up to 4.50 wt% of As does not affect the main structural topology of mertieite-II. Mertieite-II, Pd8Sb2.5As0.5 and synthetic Pd8Sb3 are isotypic compounds. The crystal structures of synthetic Pd8Sb3 and natural mertieite-II, Pd8Sb2.5As0.5, can be derived from the hexagonal close packing by filling additional layers between the close-packed 36 layers. The structure consists of Sb and (Sb,As) triangular 36, Pd triangular 36 and Pd pentagonal-triangular 5.33 layers. Stacking of Sb-, (Sb,As)- and Pd-nets along the z axis caused extension of the unit cell. It contains a total of 36 layers: six Sb1-nets, six (M1,As1)-nets, 12 Pd1-nets and 12 (Pd1,Pd3,Pd4)-nets.