Structure and Ion Mobility in MA₃F₁₇ 2HF
(M = Li, Na; M' = NH₄ , Rb, Cs; A = Zr, Hf) Compounds

I. A. Tkachenko, A. V. Gerasimenko, V. Ya. Kavun, T. F. Antokhina,
R. L. Davidovich, and V. I. Sergienko

Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia

Received February 27, 2003

Abstract—The structure and dynamics of the fluoride subsystem in the compounds described as ₃F₁₇
2HF, namely, Na(NH₄)₄Zr₃F₁₇ 2HF (I), NaCs₄Hf₃F₁₇ 2HF (II), Li(NH₄)₄Zr₃F₁₇ 2HF (III), and LiRb₄Zr₃F₁₇
2HF (IV), were studied using X-ray crystallography and NMR. The crystals belong to the monoclinic system,
space group P2₁/m (I, II) or P2₁/n (III, IV). According to the obtained results, the compounds are isostructural
within one space group. The structures of all four compounds are layered. The [₃F₁₇ 2HF layers alter-
nate with layers of M' cations. The ion motion dynamics was studied, and the types of motions were determined.
The relationship between the compound structure and the dynamic properties of the fluoride sublattice was con-
sidered.

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