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First Observation of an Inverse Ruddlesden‐Popper Series: ( A 3 n +1 ON n −1 )Bi n +1 with A = Sr, Ba and n = 1, 3
Author(s) -
Gäbler Frank,
Prots Yurii,
Niewa Rainer
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200600248
Subject(s) - bismuth , octahedron , alkaline earth metal , crystallography , inverse , metal , oxide , nitrogen , crystal structure , materials science , chemistry , analytical chemistry (journal) , metallurgy , geometry , mathematics , chromatography , organic chemistry
Single crystals ((Ba 0.78(1) Sr 0.22 ) 4 O)Bi 2 and ((Ba 0.62(1) Sr 0.38 ) 10 N 2 O)Bi 4 were successfully prepared from melt beads of Ba, Sr, and Bi in nitrogen atmosphere with oxygen impurities. The phases can be prepared in single phase from the appropriate mixtures of alkaline‐earth metal, bismuth, and bismuth oxide upon heating in pure nitrogen atmosphere. ((Ba 0.78(1) Sr 0.22 ) 4 O)Bi 2 crystallizes in the K 2 NiF 4 structure type (space group I 4/ mmm , No. 139, a = 522.34(5) pm, c = 1844.0(2) pm, Z = 2, R gt (F) = 0.039) with layers of vertex‐sharing octahedra ((Ba,Sr) 4/2 Ba 2 O). ((Ba 0.62(1) Sr 0.38 ) 10 N 2 O)Bi 4 crystallizes as an isotype of Sr 4 Ti 3 O 10 (space group I 4/ mmm , No. 139, a = 531.3(1) pm, c = 3983.2(4) pm, Z = 2, R gt (F) = 0.050) containing slabs of three layers of vertex‐sharing octahedra further connected via corners. These compounds are interpreted in terms of members of an inverse Ruddlesden‐Popper series with the general formula n ( A 3 ON n −1 )Bi · A Bi or ( A 3 n +1 ON n −1 )Bi n +1 , respectively, with n = 1, 3. Partial order of the alkaline‐earth metal ions is analyzed.