The crystal structure of ramsdellite, MnO2, was refined using time-of-flight powder neutron diffraction data and the Rietveld method in order to assess the effects of reduction in cathodic battery materials. For the first time, we present a refined structure for “groutellite,” a heretofore poorly characterized phase with ideal formula (Mn4+0.5Mn3+0.5)O1.5(OH)0.5. “Groutellite” is generated synthetically as an intermediate compound during the reduction of ramsdellite to groutite (MnOOH), and it also occurs as an intergrowth in certain natural specimens of ramsdellite. The Jahn-Teller distortions in “groutellite” are confined to the a-c plane, and they result in a 6.8% unit-cell volume increase relative to ramsdellite. The Mn-O bond lengths refined for “groutellite” are consistent with the replacement of half of the Mn4+ and O2- in ramsdellite by Mn3+ and (OH)-, respectively. In addition, the hightemperature behaviors of ramsdellite and “groutellite” were investigated by temperature-resolved synchrotron powder X-ray diffraction from 298 to 720 K. Rietveld refinements revealed a gradual thermal expansion of the groutellite structure to ∼450 K. At higher temperatures, the unit-cell volume gradually decreased, primarily as a result of a decrease in c.