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The ternary arsenides RE2/3Zn2As2 (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements in NaCl/KCl salt fluxes and were characterized by powder X-ray diffraction. The Ce2/3Zn2As2 structure was refined on the basis of single-crystal X-ray diffractometer data: CaAl2Si2 type, P¯3m1, Z = 1, a = 417.17(6), c = 703.7(1) pm, wR2 = 0.0353, 211 F2 values, 11 variables, SOF(Ce) = 62.9(5) %. The zinc and arsenic atoms form a two-dimensional network of edge-sharing ZnAs4/4 tetrahedra with Zn-Asdoi:10.1515/znb-2011-0302 fatcat:rclk2j2aszbrvbr6lp3xuxczl4