The synthesis and complex anion-vacancy ordered structure of La0.33Sr0.67MnO2.42

The low-temperature topotactic reduction of La0.33Sr0.67MnO3 with NaH results in the formation of La0.33Sr0.67MnO2.42. A combination of neutron powder and electron diffraction data show that La0.33Sr0.67MnO2.42 adopts a novel anion-vacancy ordered structure with a 6-layer OOTOOT' stacking sequence of the ‘octahedral’ and tetrahedral layers (Pcmb, a=5.5804(1) Å, b=23.4104(7) Å, c=11.2441(3) Å). A significant concentration of anion vacancies at the anion site, which links neighbouring ‘octahedral’ layers means that only 25% of the ‘octahedral’ manganese coordination sites actually have 6-fold MnO6 coordination, the remainder being MnO5 square-based pyramidal sites. The chains of cooperatively twisted apex-linked MnO4 tetrahedra adopt an ordered -L–R–L–R- arrangement within each tetrahedral layer. This is the first published example of a fully refined structure of this type which exhibits such intralayer ordering of the twisted tetrahedral chains. The rationale behind the contrasting structures of La0.33Sr0.67MnO2.42 and other previously reported reduced La1−xSrxMnO3−y phases is discussed.

Graphical AbstractThe topotactic reduction of the perovskite phase La0.33Sr0.67MnO3 with NaH yields La0.33Sr0.67MnO2.42(3), which adopts a novel anion vacancy ordered structure with a 6-layer OOTOOT' stacking sequence of the ‘octahedral’ and tetrahedral layers. The anion site that links the neighbouring octahedral layers is partially occupied so only 25% of the ‘octahedral’ manganese sites actually have 6-fold MnO6 coordination.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Topotactic reduction with NaH to form a mixed valent Mn2+/Mn3+ phase. ► Novel layered anion-vacancy ordered structure. ► Comparison to related brownmillerite structure types.