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The Inverse Perovskite Nitrides (Sr 3 N 2/3– x )Sn, (Sr 3 N 2/3– x )Pb, and (Sr 3 N)Sb: Flux Crystal Growth, Crystal Structures, and Physical Properties
Author(s) -
Pathak Manisha,
Stoiber Dominik,
Bobnar Matej,
Ormeci Alim,
Prots Yurii,
Niewa Rainer,
Höhn Peter
Publication year - 2018
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.201700368
Subject(s) - tin , antimony , nitride , crystallography , analytical chemistry (journal) , perovskite (structure) , nitrogen , metal , chemistry , antimonide , crystal structure , materials science , inorganic chemistry , nanotechnology , metallurgy , organic chemistry , layer (electronics) , chromatography
Black single crystals with metallic luster of (Sr 3 N 2/3– x ) E ( E = Sn, Pb) and (Sr 3 N)Sb were grown in lithium flux from strontium nitride, Sr 2 N, and tin, lead, or antimony, respectively. Nitrogen deficiency in the tin and the lead compound is a result of the higher ionic charge of the tetrelide ions E 4– as compared to the antimonide ion Sb 3– . In contrast to microcrystalline samples from solid state sinter reactions obtained earlier, the flux synthesis induces nitrogen order in the nitrogen deficient tetrelides. The antimony compound crystallizes as inverse cubic perovskite [ a = 517.22(5) pm, Z = 1, space group Pm 3 m , no. 221] with fully occupied nitrogen site, whereas the nitrogen deficient tin and lead compounds exhibit partially ordered arrangements and a certain phase width in respect to nitrogen contents. For the tetrelides, the nitrogen order leads to a cubic 2 × 2 × 2 superstructure [ E = Sn: a = 1045.64(8) pm for x = 0, a = 1047.08(7) pm for x = 0.08; and E = Pb: a = 1050.7(1) pm for x = 0, space group Fm 3 m , no. 225] as derived from single‐crystal X‐ray diffraction data. The metallic tetrelides show diamagnetic behavior, which is consistent with electronic structure calculations.