New triple molybdate Rb2AgIn(MoO4)3: synthesis, framework crystal structure and ion‐transport behaviour

A new triple molybdate, Rb2Ag1+3xIn1–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+3xIn1–x(MoO4)3 (x ≈ 0.004) is of a new type crystallizing in the centrosymmetric space group Rc [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. The new material Rb2Ag1+3xIn1–x(MoO4)3 (0 ≤ x ≤ 0.02) extends the series of rhombohedral framework molybdates with a ∼ 10 Å and long c axes. The compound 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.