The phase Na{sub 4}Zr{sub 6}Cl{sub 16}Be is obtained in quantitative yield from the reaction of Zr powder, ZrCl{sub 4}, NaCl, and Be flakes in a sealed Ta container at 800{degree}C. A different, isostructural group of phases Cs{sub 3}Zr{sub 6}Cl{sub 16}C, Cs{sub 3}Zr{sub 6}Cl{sub 16}B, and Cs{sub 4}Zr{sub 6}Cl{sub 16}Be were similarly obtained in {approx}90% yield from analogous reactions with CsCl, graphite, amorphous boron, etc.; reasonable yields of the first two occurred only when somewhat overreduced conditions were employed. The two structure types were established by single-crystal x-ray diffraction means for the following refined compositions: Na{sub 3.9(1)}Zr{sub 6}Cl{sub 16}Be, space group Pcmm, Z = 4, a = 13.251 (1) {angstrom}, b = 14.319 (1) {angstrom}, c = 14.092 (2) {angstrom} R = 4.3%, R{sub w} = 3.8%, Cs{sub 3.04(3)}Zr{sub 6}Cl{sub 16}C, space group P2{sub 1}/n, Z = 4, a = 11.032 (2) {angstrom}, b = 11.851 (3) {angstrom}, c = 12.473 (3) {angstrom}, {beta} = 108.01 (2){degree}, R = 6.2%, R{sub w} = 6.8%. Both structures contain puckered layers formed from Zr{sub 6}Cl{sub 12}-type clusters with Cl{sup a-a} atoms bridging four vertices into sheets plus two terminal Cl{sup a} occupying single trans positions, viz, {infinity}{sup 2}(Zr{sub 6}Cl{sub 12}Z)Cl{sup a-a}{sub 4/2}Cl{sup a}{submore » 2}, where the interstitial Z = Be, B, or C occupies all cluster centers. The cluster layers are separated and puckered to different degrees in order to provide suitable chlorine polyhedra between them to accommodate the cations. The latter fractionally occupy irregular sites that are minimally six- (Na{sup +}) or seven-coordinate (Cs{sup +}). The 15-electron cluster in the cesium salt exhibits shorter Zr-Zr and Zr-Zr distances than analogous 14-electron examples. 24 refs., 7 figs., 5 tabs.« less
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