Polybismuth anions. Synthesis and crystal structure of a salt of the tetrabismuthide(2-) ion, Bi/sub 4//sup 2 -/. A basis for the interpretation of the structure of some complex intermetallic phases

Journal Article · Sat Oct 01 00:00:00 EDT 1977 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50176a011· OSTI ID:7285889

Cisar, A; Corbett, J D

The intermetallic compounds K/sub 5/Bi/sub 4/ and K/sub 3/Bi/sub 2/ have been found to react with solutions of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8)hexacosane (2,2,2-crypt) in ethylenediamine to form deep green-red dichroic solutions. These spontaneously deposit black crystals of the compound 2,2,2-crypt--potassium tetrabismuthide(2-), C/sub 18/H/sub 36/N/sub 2/O/sub 6/K/sup +/)/sub 2/Bi/sub 4//sup 2 -/, with more reduced compounds remaining in solution. This compound crystallizes in the triclinic space group P anti l with lattice constants a = 11.604 (4) A, b = 11.796 (4) A, c = 11.096 (3) A, ..cap alpha.. = 98.12 (3)/sup 0/, ..beta.. = 98.02 (3)/sup 0/, and ..gamma.. = 61.37 (3)/sup 0/ with one formula unit per cell. Three-dimensional x-ray data were collected from two crystals on an automated diffractometer using monochromatic Mo K..cap alpha.. radiation, and the structure was deduced by conventional heavy atom techniques. Positional and anisotropic thermal parameters of the 29 independent nonhydrogen atoms refined by full matrix least squares using 2704 unique observed (I > 3sigma/sub 1/) reflections to R = 0.121, R/sub w/ = 0.147. Four of the carbon atoms in the ligand exhibit extremely anisotropic thermal parameters, which effect was resolved and refined in terms of pairs of disordered atoms at 0.50 occupancy. The Bi/sub 4//sup 2 -/ anion effectively exhibits D/sub 4//sub h/ symmetry with observed bond lengths of 2.936 (2) and 2.941 (2) A and bond angles of 89.85 (6) and 90.15 (6)/sup 0/. The bonding is considered to be the same as in the isoelectronic Te/sub 4//sup 2 +/. The Bi/sub 4//sup 2 -/ ion provides a useful starting point for the interpretation of the square metal groups found in the isostructural Ca/sub 11/Bi/sub 10/, Ca/sub 11/Sb/sub 10/, and Ho/sub 11/Ge/sub 10/.

• Research Organization: Ames Lab., IA
• OSTI ID: 7285889
• Journal Information: Inorg. Chem.; (United States), Vol. 16:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BISMUTH COMPOUNDS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
ORGANIC NITROGEN COMPOUNDS
POTASSIUM COMPLEXES
BISMUTH ALLOYS
INTERMETALLIC COMPOUNDS
POTASSIUM ALLOYS
ALKALI METAL COMPLEXES
ALLOYS
COMPLEXES
ORGANIC COMPOUNDS
SYNTHESIS
400201* - Chemical & Physicochemical Properties