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The crystal structure of barium hydroxide iodide tetrahydrate Ba(OH)I · 4 H 2 O (space group  P [unk], No. 2,  Z  = 2,  a  = 628.1(1) pm,  b  = 806.1(2) pm,  c  = 811.8(1) pm,  α  = 90.47(1)°,  β  = 106.87(1)°, and  γ  = 90.97(1)°, final  R 1 = 0.0398 ( I  &gt; 2 σ ( I ) for 780 unique reflections) was redetermined by single-crystal neutron diffraction studies. Each of the four crystallographically different H 2 O molecules serves as donor of a very weak hydrogen bond to adjacent I –  ions and quite a strong one to an OH –  ion or another H 2 O molecule (H 2 O II). Hence, the hydrate H 2 O molecules are extremely asymmetrically bound. The difference of the two internal O–H distances of the H 2 O molecules Δ r  O–H  reaches 8.1 pm at the most. As a consequence, the stretching modes of the H 2 O molecules are fully decoupled. The OH –  ion donates a very weak O–H – ···I hydrogen bond and accepts three HO–H···OH –  bonds. The different strength of the hydrogen bonds is discussed with respect to the acceptor capability of the hydrogen-bond acceptor groups and the various OH frequency versus  r  O–H  and  r  H···Y  hydrogen-bond distance correlation curves reported in the literature.

Neutron single-crystal study of barium hydroxide iodide tetrahydrate, a compound with most strongly distorted hydrate H 2 O molecules