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The crystalline silver ion conductor Ag 8 I 4 V 2 O 7  has recently been identified as the annealing product of the ion conducting glass 4 AgI–2 Ag 2 O–V 2 O 5 . Single crystals of the same compound are synthesised directly from the melt. Ag 8 I 4 V 2 O 7  crystallises in  P [unk]2 m  (No. 189) with  a  = 12.595(2) Å,  c  = 9.119(2) Å and  Z  = 3. The crystal structure is refined to a residual  R  1  = 0.040 for 498 unique reflections with  F  o  ≥ 4 σ ( F  o ) and sin  θ / λ  ≤ 0.60 Å −1 .

Crystal structure and Ag + conductivity of the solid electrolyte Ag 8 I 4 V 2 O 7