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The hydrogen-bond arrangement within crystalline 2,3,6,7,10,11-hexahydroxytriphenylene tetrahydrate (HHTP·4H2O) undergoes an order-disorder transition at 240 K, as evidenced by the emergence and disappearance of systematic absence violations in variable-temperature single-crystal X-ray diffraction measurements. The low-temperature ordered phase is polar with ferroelectric coupling between neighbouring one-dimensional ice-like columns of hydrogen-bonded H2O molecules. At temperatures above 240 K the material adopts a paraelectric state characterised by the absence of long-range ordering between column polarisations. We discuss the mapping of this phase transition onto the problem of frustration on the canonical Ising square lattice, and suggest that HHTP·4H2O is an obvious candidate for exploring switchable ferroelectric behaviour in confined ices.

Structural investigation of a hydrogen bond order–disorder transition in a polar one-dimensional confined ice