The vanadate garnet Ca2NaCd2V3O12: a single-crystal X-ray diffraction study.

Abstract

Single crystals of the vanadate garnet Ca2NaCd2V3O12 (dicalcium sodium dicadmium trivanadate) were synthesized using the floating-zone method and the crystal structure was investigated using single-crystal X-ray diffraction. We considered the effectiveness of substitution of the Y-site cation with reference to previous structural studies of vanadate garnets. The structures of vanadate garnets are subject to geometric constraints similar to those of silicate garnets. These constraints force the tetrahedral-dodecahedral shared edge length in vanadate garnets to become shorter than the unshared dodecahedral edge length, as in ugrandite (uvarovite, grossular and andradite) garnets. However, the vanadate garnet Ca2NaCd2V3O12 exhibits the normal structural feature, similar to pyralspite (pyrope, almandine and spessartine) garnets, namely that the dodecahedral-dodecahedral shared edge length is shorter than the unshared dodecahedral edge length. With increasing ionic radius of the Y-site cation, the atomic coordinates x, y and z of oxygen adopt values which satisfy Pauling's third rule.