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Ag 9 I(GeO 4 ) 2 – Containing Two‐dimensionally Linked [IAg 12 ] Metallo Complexes
Author(s) -
Pitzschke Dragan,
Curda Jan,
Jansen Martin
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900148
Subject(s) - stoichiometry , ion , analytical chemistry (journal) , conductivity , ionic conductivity , oxygen , crystallography , crystal structure , atmospheric temperature range , materials science , chemistry , physics , organic chemistry , chromatography , electrode , meteorology , electrolyte
Ag 9 I(GeO 4 ) 2 was obtained for the first time by reacting a stoichiometric mixture of Ag 2 O, AgI, and GeO 2 , at elevated oxygen pressures, adding a small portion of distilled water. The synthesis was done at 480 °C and 110 MPa of oxygen pressure. It crystallizes in space group C 2/ m , with the unit cell dimensions a = 17.3736(9) Å, b = 6.9177(4) Å, c = 5.7176(3) Å, β = 105.501(3)°, V = 662.18(6) Å 3 , and Z = 2. The structure refinement was based on 638 independent reflections and resulted in R 1 = 6.26 %. The crystal structure consists of isolated (GeO 4 ) 4– ions and [IAg 12 ] metallo complexes, the latter are interconnected through each two common edges and corners corresponding to [IAg 6/1 Ag 6/2 ], thus forming infinite layers within the (100) plane. The Ag/I slabs are stacked perpendicular to the a ‐axis with an interlayer distance of about 3.4 Å. The (GeO 4 ) 4– anions are located in the gaps between the silver iodide layers. According to the results of impedance measurements, Ag 9 I(GeO 4 ) 2 is a good silver ion conductor. The compound shows an increase in the ionic conductivity in the temperature range of 30 to 310 °C, and has a silver ion conductivity of 1.1 × 10 –3 Ω –1 cm –1 at room temp. The activation energy for silver ion conduction is 0.35 eV, in the temperature range from 25 to 190 °C.