A low-temperature topotactic route is used to assemble metal-anion arrays within a perovskite host. Ion exchange between RbLaNb 2 O 7 and CuX 2 (X ) Cl, Br) results in a new set of layered copperoxyhalide perovskites, (CuX)LaNb 2 O 7 . Rietveld structural analysis of X-ray powder diffraction data confirms the formation of a two-dimensional copper-halide network in the double-layered perovskite interlayer. This new structure type contains unusual CuO 2 X 4 octahedra that corner-share with NbO 6 octahedra from the perovskite slab and edge-share with each other along all four equatorial edges. Magnetic susceptibility measurements show that both products exhibit antiferromagnetic transitions below 40 K. Additionally, these materials are found to be low-temperature phases, decomposing completely by 700°C. The synthetic approach described in this work is significant in that it demonstrates how host structures can be used as templates in the directed low-temperature assembly of extended metal-anion arrays.

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The current definition of samarskite-group minerals suggests that ishikawaite is a uranium rich variety of samarskite whereas calciosamarskite is a calcium rich variety of samarskite. Because these minerals are chemically complex, usually completely metamict, and pervasively altered, their crystal chemistry and structure are poorly understood. Warner and Ewing (1993) proposed that samarskite is an A 3+ B 5+ O 4 mineral with an atomic arrangement related to a-PbO 2 . X-ray diffraction analyses of the recrystallized type specimen of ishikawaite and the Ca-rich samarskite reveal that they have the same structure as samarskite-(Y) recrystallized at high temperatures. Electron microprobe analyses show that the only significant difference between samarskite-(Y), ishikawaite, and calciosamarskite lies in the occupancy of the A-site. The A-site of samarskite-(Y) is dominated by Y+REE whereas the A-site of ishikawaite is dominantly U+Th and calciosamarskite is dominantly Ca. Additionally, a comparison of these data to those of Warner and Ewing (1993) show that in several cases Fe 2+ or Fe 3+ are dominant in the A-site. We propose that the name samarskite-(REE+Y) should be used when one of these elements is dominant and that the mineral be named with the most abundant of these elements as a suffix. The name ishikawaite should be used only when U+Th are dominant and the name calciosamarskite should only be used when Ca is the dominant cation at the A-site. Finally, because of the inability to quantify the valence state of iron in these minerals, the exact nature of the valence state of iron in these minerals could not be determined in this study.