Abstract
Reactions of Zr, ZrCl{sub 4}, and MnCl{sub 2} in welded Ta containers at 800 {degrees}C produce the title phase in major amounts. A comparable electronic and structural configuration is also found with interstitial boron, but not in isostructural compounds with other interstitial or alkali metal atoms. The crystal structure of Cs{sub 3}(ZrCl{sub 5})[Zr{sub 6}(Mn)Cl{sub 12}]Cl{sub 6/2} was established by single-crystal diffraction (R3c, Z = 6, a = 12.8924(1) {angstrom}, c = 35.187 (6) {angstrom}, R/R{sub w} = 1.9/2.3% for 920 data to 20 = 60{degrees}). The structure contains a three-dimensional array of 18-electron Zr{sub 6}(Mn)Cl{sub 12} clusters interbridged by 6/2 Cl{sup a-a} atoms at zirconium vertices. This represents a sixth independent structure type for M{sub 6}X{sub 15} bridged cluster networks. The structure derives from a ReO{sub 3}-like primitive lattice of the cubic Nb{sub 6}F{sub 15} structure with linear bridges that has been given a {open_quotes}trigonal twist{close_quotes} about [111] to form a rhombohedral (tilted) perovskite arrangement with the novel ZrCl{sub 5}{sup {minus}} at the body center. This new D{sub 3h} anion does not share halogen with the rest of the structure and appears to be stabilized by a particularly good fit within the network. A double ccp cluster arrangement along c{submore » H} provides for a coherent intercluster bridging arrangement. The cesium cations necessitated by the anionic network and by the CsZrCl{sub 5} component are bound in well-suited 12-coordinate sites among the chlorines.« less
Published Version
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