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The title compound, 2C5H6N+·TeF5·0.5Te2F6O22−, contains two anions, [TeF5] and [Te2O2F6]2−. The [Te2O2F6]2− anions are involved in H...F/O bonding with the pyridinium cations. Crystallographically imposed inversion leads to mol­ecular Cs symmetry for the [Te2O2F6]2− anions. Extended chains of inversion-related pyridinium cations are built up by π–π inter­actions.
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