The Inverse Perovskite Nitrides (Sr3N2/3–x)Sn, (Sr3N2/3–x)Pb, and (Sr3N)Sb: Flux Crystal Growth, Crystal Structures, and Physical Properties

Abstract

Black single crystals with metallic luster of (Sr3N2/3–x)E (E = Sn, Pb) and (Sr3N)Sb were grown in lithium flux from strontium nitride, Sr2N, 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 E4– as compared to the antimonide ion Sb3–. 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 Pm3m, 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 Fm3m, no. 225] as derived from single‐crystal X‐ray diffraction data. The metallic tetrelides show diamagnetic behavior, which is consistent with electronic structure calculations.