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Phenol hemihydrate, C 5 H 5 OH·0.5H 2 O, crystallizes in the space group Pbcn , Z = 8. The previously published crystal structure [CSD refcode PHOLHH; Meuthen &amp; von Stackelberg (1960 ▸). Z. Elektrochem . 64 , 387-390] is shown to be incorrect. Pairs of phenol mol-ecules, related by an inversion centre, are bridged by one water mol-ecule via O-H⋯O hydrogen bonds; an extended R  4  4 (8) hydrogen-bonded motif links these inversion dimers into chains parallel to the c axis. Packing of the chains is achieved by weaker T-shaped C-H⋯π inter-actions between nearest neighbour phenol mol-ecules in the bc plane. Analysis of the thermal expansion and parameterization with a Debye model in terms of the linear elastic moduli shows that the c axis is ∼3 times stiffer than the two orthogonal directions.

acta crystallographica. section e, crystallographic communications

Phenol hemihydrate: redetermination of the crystal structure by neutron powder diffraction, Hirshfeld surface analysis and characterization of the thermal expansion