Cation substitution effects in the system Sr2-xBaxBi3 (0 < or = x < or = 1.3): structural distortions induced by chemical pressure.

Crystals of the composition Sr(2-x)Ba(x)Bi(3) (0 < or = x < or = 1.3) have been synthesized from the elements and were characterized by single-crystal and powder X-ray diffraction methods. The compounds crystallize for x = 0, 0.45, 0.86, 1.08, 1.28 in the structure type of the parent compound Sr 2Bi 3 with space group Pnna (No. 52) and Z = 4. Substitution of Sr by Ba leads to a site preference for Ba. The anionic Bi substructures in the pseudoternary system simultaneously distort under remarkable elongation of one distinct Bi-Bi contact. Magnetic measurements for samples with x = 0, 0.45 and 1.08 reveal superconducting transitions at low temperatures. Linear muffin-tin orbital band structure calculations of Sr(2)Bi(3) show strong cation-anion interactions that greatly stabilize the structure. Besides showing characteristics of a typical metal, the band structure plot unveils the co-instantaneous occurrence of flat and steep bands around the Fermi level indicative for superconductivity.