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

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

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.

Translated title of the contribution
Bi12,86Ni4Br6 and Bi12,86Ni4I6
Subhalides with alternating intermetallic and salt-like layers

Details

Original languageGerman
Pages (from-to)453-462
Number of pages10
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume625
Issue number3
Publication statusPublished - 1999
Peer-reviewedYes
Externally publishedYes

External IDs

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

Keywords

ASJC Scopus subject areas

Keywords

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