Schäferite, NaCa2Mg2(V5+O4)3; palenzonaite, NaCa2Mn22+(V5+O4)3; berzeliite, NaCa2Mg2(As5+O4)3; and manganberzeliite, NaCa2Mn22+(As5+O4)3, are cubic minerals with garnet structures (space group Iad) in which tetrahedrally coordinated V5+ and/or As5+ at the Z site are charge balanced by disordered Na+ and Ca2+ at the X site, and divalent Mg2+ and Mn2+ cations at the octahedrally coordinated Y site. The crystal chemistry of palenzonaite (from the Molinello and Gambatesa mines, Italy, and the Fianel mine, Switzerland), berzeliite (from Långban, Sweden, and Montaldo, Italy), and manganberzeliite (from Varenche, Italy, and the Gozaisho mine, Japan) were studied by electron microprobe analysis and single-crystal X-ray diffraction methods. Structure refinements converged to R1 values of 1.36–2.42%. The tetrahedral site in these garnet structures is mainly occupied by pentavalent As5+ or V5+ (only up to about 20% randomly distributed Si4+ is present). Charge balance is maintained by variations in the Ca/Na ratio at the X site. Heterovalent substitution (Na+ ↔ Ca2+) at the distorted square antiprism X site in vanadate- and arsenate-bearing garnets allows full occupancy of the octahedral Y site by divalent cations (primarily Mg2+ and Mn2+). There is a positive correlation between the <Z–O> and <Y–O> bond lengths and the mean ionic radii of the substituent elements, but there is no correlation between the <X–O> bond length and the variable Na/Ca site occupancy. The ionic radii of octahedrally coordinated Mg2+ and Mn2+ are such that the shared octahedral–dodecahedral edges are similar in length to the unshared octahedral edges, which is a measure of lattice distortion in garnet structures.

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