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{[Co(pht)(bpy)(H2O)2]·2H2O}n (P2/n) single crystals (where pht is phthalate and bpy is 4,4'-bi­pyridine) dehydrate in a topotactic fashion into an anhydrate formulated as [Co(pht)(bpy)(H2O)2]n, which organizes in the ortho­rhom­bic system (Pmn21) in a disordered fashion, where two mirror-related 0.50:0.50 occupancy two-dimensional planar substructures are mirrored in a plane perpendicular to [100]. These two-dimensional substructures are also present in the parent hydrate, and have been found in topologically related structures with different anions and cations.
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