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In the title compound, C36H25F6O2P2+·I3, hydrogen-bonded [{(p-FC6H4)3PO}2H]+ dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I—I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter-ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å−3. The inclusion of two low-occupancy I-atom sites (total 1.7%), which can be inter­preted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å−3. The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin.
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