Abstract
A new triple molybdate, Rb2Ag1+3x
In1–x
(MoO4)3 (0 ≤ x ≤ 0.02), was found in the course of a study of the system Rb2MoO4–Ag2MoO4–In2(MoO4)3 and was synthesized as both powders and single crystals by solid-state reactions and spontaneous crystallization from melts. The structure of Rb2Ag1+3x
In1–x
(MoO4)3 (x ≈ 0.004) is of a new type crystallizing in the centrosymmetric space group R\overline{3}c [a = 10.3982 (9), c = 38.858 (4) Å, Z = 12 and R = 0.0225] and contains (In,Ag)O6 octahedra and distorted Ag1O6 trigonal prisms linked by common faces to form [Ag(In,Ag)O9] dimers connected to each other via MoO4 tetrahedra into an open three-dimensional (3D) framework. Between two adjacent [Ag(In,Ag)O9] dimers along the c axis, an extra Ag2O6 trigonal prism with about 1% occupancy was found. The Ag1O6 and Ag2O6 prisms are located at levels of z ≈ 1/12, 1/4, 5/12, 7/12, 3/4 and 11/12, and can facilitate two-dimensional ionic conductivity. The 12-coordinate Rb atoms are in the framework cavities. The structure of Rb2AgIn(MoO4)3 is a member of the series of rhombohedral 3D framework molybdate structure types with a ≈ 9–10 Å and long c axes, which contain rods of face-shared filled and empty coordination polyhedra around threefold axes. Electrical conductivity of ceramics is measured by impedance spectroscopy. Rb2AgIn(MoO4)3 undergoes a `blurred' first-order phase transition at 535 K with increasing electrical conductivity up to 1.1 × 10−2 S cm−1 at 720 K. Thus, the compound may be of interest for developing new materials with high ionic conductivity at elevated temperatures.
Funder
Ministry of Science and Higher Education of the Russian Federation
Russian Foundation for Basic Research
Publisher
International Union of Crystallography (IUCr)
Subject
Materials Chemistry,Inorganic Chemistry,Physical and Theoretical Chemistry,Condensed Matter Physics
Cited by
8 articles.
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