Bi12,86Ni4Br6 und Bi12,86Ni4I6: Subhalogenide mit intermetallischen und salzartigen Schichtpaketen in alternierender Abfolge

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

  • Michael Ruck - , Karlsruher Institut für Technologie (Autor:in)

Abstract

The reaction of bismuth and nickel with bromine or iodine at 730 K yields black, air insensitive, needle shaped crystals of the ternary subhalides Bi12,86Ni4X6 (X = Br, I). The isotypic compounds crystallize in the orthorhombic space groups Immm with a = 405.69(6) pm, b = 874.00(8) pm, c = 3744.7(4) pm for X = Br, and a = 410.05(5) pm, b = 912.84(7) pm, c = 3826.7(3) pm for X = I. The crystal structures contain characteristic fragments of the intermetallic phase Bi3Ni: chains consisting of face sharing monocapped trigonal prisms of bismuth atoms with a nickel atom in the center of each prism. The chains form corrugated layers which are separated by halogen atoms and oligomeric [BinX4n+2] units of varying length. The halogenobismutate(III) units consist of trans-edge-sharing [BiX6] octahedra. They are disordered within the crystal structures. The non-integer stoichiometric coefficients of Bi12,86Ni4X6 are due to the metric adjustment between the ionic and intermetallic parts of the structure. Extended Hückel calculations indicate, that the partial oxidation of the intermetallic phase causes a strengthening of the chemical bonding within the Bi3Ni chains. The subiodide Bi12,86Ni4I6 is paramagnetic and shows ferromagnetic ordering below 25 K.

Details

OriginalspracheDeutsch
Seiten (von - bis)453-462
Seitenumfang10
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang625
Ausgabenummer3
PublikationsstatusVeröffentlicht - 1999
Peer-Review-StatusJa
Extern publiziertJa

Externe IDs

ORCID /0000-0002-2391-6025/work/166325877

Schlagworte

ASJC Scopus Sachgebiete

Schlagwörter

  • Bismuth nickel subhalide, Chemical bonding, Crystal structure, Magnetic properties