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Powder neutron diffraction studies on CrOOH-type zero-dimensional H-bonded crystals

Abstract Exceptionally large geometric isotope effects ΔR(O…O) on deuteration, in the range of two to three times the maximum value in the other hydrogen-bonded crystals, have earlier been reported for α-CrOOH, β-CrOOH and α-CoOOH. In order to reinvestigate these apparently anomalous large geometric isotope effects, powder neutron diffraction studies have been done. For α-CrOOH and β-CrOOH(D), the earlier reported R(O…O) distances at room temperature were confirmed, with smaller e.s.d.'s than in the earlier works. Furthermore, it has been found that the structure of α-CrOOD is not the same as that of α-CrOOH at room temperature, in accordance with a structural phase transition newly found above room temperature. The magnitude of ΓR for α-CrOOH and β-CrOOH seems to be not as large as reported earlier, but in the maximum range (at most 0.05 Å).