Syntheses and structures of new phases AeM(x)In(4-x) (Ae = Sr, Ba; M = Mg, Zn): Size effects and site preferences in BaAl4-Type structures

TitleSyntheses and structures of new phases AeM(x)In(4-x) (Ae = Sr, Ba; M = Mg, Zn): Size effects and site preferences in BaAl4-Type structures
Publication TypeJournal Article
Year of Publication2007
AuthorsLi B, Corbett JD
Journal TitleInorganic Chemistry
Volume46
Pages8812-8818
Date PublishedOct
Type of ArticleArticle
ISBN Number0020-1669
Accession NumberISI:000250009600059
Keywordschemistry, crystal-structure, electronic-structure, elements, intermetallic compounds, metals, NETWORK, solid-state, stability, substitution
Abstract

The title phases were synthesized via high-temperature solid-state methods and structurally characterized by single-crystal X-ray diffraction. The phase widths of both SrMg(x)ln(4-x) (0.85 <= x <= 1.53) and BaMg(x)ln(4-x) (0 <= x <= 1.79) are consistent with size matches between Ae and the encapsulating Win cages. All compounds crystallize in body-centered tetragonal BaAl4-type structure (I4/mmm, Z = 2) except that SrMg(x)ln(4-x), 0.85 <= x <= 1.24, occurs in the lower-symmetry space group (l (4) over bar m2, Z = 2) and the atoms are all ordered at the composition SrMgIn3. The substitution of the effectively smaller Mg or Zn atoms into the indium sublattice of the monoclinic SrIn4 (C2/m) dramatically changes the structure into the tetragonal BaAl4-type structure. Compared with the Mg compounds in which all Mg occupy the basal 4d crystallographic site, Zn occupies the other 4e (apical) site in both BaZn0.79(2)In3.21 and SrZn1.00(4)In3.00. These differences are related to the interplay of size and. electronic factors. The latter may be expressed by not only electronegativities but also total energies according to linear muffin-tin-orbital calculations.

DOI10.1021/ic701127f
Alternate JournalInorg. Chem.