Abstract
Abstract Single crystals of Ca2Co5.66Zn11.34, Ca2Co4.62Zn12.38 and Ca2Co2.36Zn14.64 were obtained from reactions of the elements in sealed tantalum ampoules. The crystal structures were refined from single-crystal X-ray diffractometer data: Th2Zn17 type, R 3 ‾ $\overline{3}$ m, a = 879.93(7), c = 1282.81(11) pm, wR = 0.0394, 432 F 2 values, 25 variables for Ca2Co5.66Zn11.34, a = 886.0(4), c = 1293.1(6) pm, wR = 492 F 2 values, 25 variables for Ca2Co4.62Zn12.38 and a = 894.62(16), c = 1307.2(3) pm, wR = 0.0463, 460 F 2 values, 24 variables for Ca2Co2.36Zn14.64. The crystal chemistry of these phases is driven by different Co/Zn mixed occupied sites. The structures are explained as a rod packing of infinite strands that are built up from pairs of interpenetrating Ca@(Co/Zn)19 and Zn1@(Co/Zn)13Ca polyhedra.
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