  Neutron and x-ray powder diffraction have been used to investigate the
crystal structures of a sample of the newly-discovered superconducting sodium
cobaltate deuterate compound with composition Na0.31(3)CoO2o1.25(2)D2O and its
anhydrous parent compound Na0.61(1)CoO2. The deuterate superconducting compound
is formed by coordinating four D2O molecules (two above and two below) to each
Na ion in a way that gives Na-O distances nearly equal to those in the parent
compound. One deuteron of the D2O molecule is hydrogen bonded to an oxygen atom
in the CoO2 plane and the oxygen atom and the second deuteron of each D2O
molecule lie approximately in a plane between the Na layer and the CoO2 layers.
This coordination of Na by four D2O molecules leads to ordering of the Na ions
and D2O molecules. The sample studied here, which has Tc=4.5 K, has a refined
composition of Na0.31(3)CoO2o1.25(2)D2O, in agreement with the expected 1:4
ratio of Na to D2O. These results show that the optimal superconducting
composition should be viewed as a specific hydrated compound, not a solid
solution of Na and D2O (H2O) in NaxCoO2oyD2O. Studies of physical properties
vs. Na or D2O composition should be viewed with caution until it is verified
that the compound remains in the same phase over the composition range of the
study.
