Arsenmedaite, $Mn62+As5+Si5O18(OH)$⁠, the arsenic analogue of medaite, from the Molinello mine, Liguria, Italy: occurrence and crystal structure

The new mineral species arsenmedaite, ideally $Mn62+As5+Si5O18(OH)$ , has been discovered in quartz veinlets in the braunite ore deposit of the Molinello mine, Graveglia Valley, Ne, Genova, Liguria, Italy. It occurs as orange-reddish prismatic crystals, up to 200 μm in length, with a vitreous lustre, associated with braunite, quartz, calcite, As-rich medaite, calcian rhodocrosite, talc, and ganophyllite. Electron microprobe analysis of arsenmedaite gave (in wt%): V₂O₅ = 1.84, As₂O₅ = 6.81, SiO₂ = 38.75, CaO = 0.70, MnO = 50.28, H₂O_calc = 1.42, total 99.80. On the basis of ΣMe = 12 atoms per formula unit, the chemical formula of arsenmedaite is (Mn_5.89Ca_0.10)_Σ5.99[(As_0.49V_0.17)_Σ0.66Si_5.35]_Σ6.01O_17.69(OH)_1.31. The main diffraction lines are [d in Å (relative intensity) hkl]: 3.266 (100) 081, 3.159 (72) 052, 3.094 (82) −221, 2.963 (83) 091, 2.935 (79) 211, 2.788 (68) 072, and 2.612 (98) 082. The crystal-structure study gives a monoclinic unit cell, space group P2₁/n, with a = 6.7099(3), b = 29.001(1), c = 7.5668(3) Å, β = 95.469(3)°, V = 1465.7(1) ų, Z = 4. The crystal structure has been solved and refined to R₁ = 0.062 on the basis of 3526 reflections with F_o > 4σ(F_o) and 287 parameters. Arsenmedaite is isotypic with medaite. In its crystal structure, six- to seven-fold coordinated Mn-centred polyhedra form wavy ribbons linked to TO₄ tetrahedra centred by Si and (As,V). Its formation is likely related to the late-stage circulation of As- and Mn-rich hydrothermal fluids during the final stages of the Alpine tectono-metamorphic evolution of the manganese ore deposits of Eastern Liguria.