Comparative zirconium bromide cluster chemistry. A new structure in K{sub 4}Zr{sub 6}Br{sub 18}C
- Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Reactions of ZrBr{sub 4}, Zr, ABr (A = Li-Cs, Ba), and Z (Be, B, C, Mn) mixtures with suitable compositions in sealed Ta containers have revealed 19 additional examples of A{sub x}(Zr{sub 6}Br{sub 12}Z) Br{sub y}-type phases that span 0 {le} y {le} 6. A new triclinic structure is reported for K{sub 4}Zr{sub 6}Br{sub 18}C (P{bar 1}, Z = 1, a = 10.114(2), b = 10.283(3), c = 10.374(3), {alpha} = 118.54(2), {beta} = 99.98(2), {gamma} = 104.08(2), R(F)/R{sub w} = 5.1/4.7%) and K{sub 4}Zr{sub 6}Br{sub 18}Fe. Nearly octahedral Zr{sub 6}(C)Br{sub 18}{sup 4{minus}} clusters stack in layers with K{sup +} in pseudo-tetrahedral bromine cavities on their outward surfaces. The present structure can be converted to a pseudo-C-centered monoclinic version that is related to those of Rb{sub 4}Zr{sub 6}Cl{sub 18}C (C2/m) and, more distantly, Rb{sub 5}Zr{sub 6}Cl{sub 18}B (Pnam) according to cluster size and the need for good bonding sites for the cations. A variety of other new bromide phases that form in seven known zirconium cluster chloride or iodide structure types according to powder pattern or single crystal data is also reported. Some of these demonstrate greater, lesser, or alternative cation site occupancies in the same basic structure types.
- Sponsoring Organization:
- National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
- OSTI ID:
- 653131
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 139; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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