Structural Novelties in Anionic Cluster Halide Phases. Discrete Tetrahedral A4Br+ Ions in Two New Zirconium Bromide Structures (A = Na−Cs)
- 1 December 1997
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 36 (26) , 6039-6044
- https://doi.org/10.1021/ic970818u
Abstract
Suitable reactions of ABr, Zr, ZrBr4, and an interstitial Z element in Ta containers at 850 °C afford two series of quaternary cluster phases containing A4Br3+ ions. Cubic (A4Br)2Zr6(Z)Br18 phases occur for various combinations of A = Na−Cs, Z = Be, B, H, Mn. The combination with A = K, Z = B was structurally characterized (inverse fluorite, Fm3̄m, Z = 4, a = 16.191(2) Å). The 15-e cluster exhibits the appropriate magnetic moment, and this decreases toward the diamagnetic 14-electron limit in products with potassium deficiencies, (K4-x)2Zr6Br18B, x ≤ ∼ 0.5. The tetragonal Cs4Br[Zr6(B)Br12]Br4 (P4̄21m, Z = 2, a = 12.5482(7) Å, c = 11.5610(9) Å) contains a new type of puckered M6Br16 layers with Cs4Br3+ in tunnels normal to the layers. Both examples of A4Br3+ ions have short central Br−A bonds plus three to nine more distant bromines in neighboring clusters about each A, respectively.Keywords
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