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Title: Synthesis and structural characterization of some compounds involving metal-metal bonding of tellurium, bismuth, and zirconium. [Complex with hexaoxadiazabicyclohexacosane potassium]

Technical Report ·
DOI:https://doi.org/10.2172/6549645· OSTI ID:6549645

Salts of the tritelluride(2-) and tetrabismuthide(2-) ions with the complex cation (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8)hexacosane potassium) (abbreviated crypt K/sup +/) were synthesized and their structures determined. The dark red (crypt K/sup +/)/sub 2/ Te/sub 3//sup 2 -/.en was produced by oxidation of K/sub 2/Te with an excess of tellurium and the very dark green (crypt K/sup +/)/sub 2/Bi/sub 4//sup 2 -/ was produced by the reaction of either K/sub 3/Bi, K/sub 3/Bi/sub 2/, K/sub 5/Bi/sub 4/, or KBi/sub 2/ with solvent. (Crypt K/sup +/)/sub 2/Te/sub 3//sup 2 -/.en crystallizes in the trigonal space group P3/sub 2/ with a = 12.229(1)A and c = 31.242(4)A and three formula units per cell. The Te/sub 3//sup 2 -/ ion has bond lengths of 2.692(5) and 2.720(4)A, an angle of 113.1(2)/sup 0/, and a hydrogen bond to an en molecule with d/sub Te-N/ = 3.46(6)A. (Crypt K/sup +/)/sub 2/Bi/sub 4//sup 2 -/ crystallizes in the triclinic space group P anti 1 with 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/ and one formula per cell. The structure of the more common form of stoichiometric ZrCl/sub 2/, which is isostructural with 3R-MoS/sub 2/, (R3m, with a = 3.3819(3) and c = 19.378(3)A) was refined from single crystal data. A cluster form which is isostructural with Zr/sub 6/I/sub 12/ was found and its structure determined from powder data. 6T-Zr/sub 1+x/Cl/sub 2/ was determined from an intergrown ''single'' crystal containing 3R-ZrCl/sub 2/, to be a 6-slab superstructure based on a 2H/sub b/-MoS/sub 2/ type subcell with a = 3.3791(4) and c = 38.713(7)A. Another, 18T-Zr/sub 1+y/Cl/sub 2/, found in both single crystals and powder, has an 18 slab repeat sequence with a = 3.3820(2) and c = 116.21(2)A. The third is of unknown composition and exhibits ordering along a.

Research Organization:
Iowa State Univ., Ames, IA (United States)
DOE Contract Number:
W-7405-ENG-82
OSTI ID:
6549645
Report Number(s):
IS-T-813
Country of Publication:
United States
Language:
English