Ralphcannonite, AgZn2TlAs2S6, a new mineral of the routhierite isotypic series from Lengenbach, Binn Valley, Switzerland

The new mineral species ralphcannonite, AgZn2TlAs2S6, was discovered in the Lengenbach quarry, Binn Valley, Wallis, Switzerland. It occurs as metallic black equant, isometric to prismatic crystals, up to 50 μm, associated with dufrenoysite, hatchite, realgar and baryte. Minimum and maximum reflectance data for COM wavelengths in air are [λ (nm): R (%)]: 471.1: 25.8/27.1; 548.3: 25.2/26.6; 586.6: 24.6/25.8; 652.3: 23.9/24.8. Electron microprobe analyses give (wt.%): Cu 2.01(6), Ag 8.50( 16), Zn 10.94(20), Fe 3.25(8), Hg 7.92(12), Tl 24.58(26), As 18.36(19), Sb 0.17(4), S 24.03(21), total 99.76(71). On the basis of 12 atoms per formula unit, the chemical formula of ralphcannonite is Ag0.63(2)Cu0.25(2)Zn1.35(5)Fe0.47(1)Hg0.32(2)Tl0.97(3)[As1.97(6)Sb0.01(1)]Σ1.9(8)S6.03(8). The new mineral is tetragonal, space group I4 2m, with a =9.861 (2), c= 11.125(3) Å, V= 1081.8(4) Å3, Z= 4. The main diffraction lines of the calculated powder diagram are [d(in Å), intensity, hkl]: 4.100, 85, 211; 3.471,40, 103; 2.954, 100, 222; 2.465, 24, 400; 2.460,39, 303. The crystal structure of ralphcannonite has been refined by X-ray single-crystal data to a final Ri =0.030, on the basis of 140 observed reflections [F0> 4σ(F0)]. It shows a three dimensional framework of (Ag,Zn)- centred tetrahedra (1 M1 + 2 M2), with channels parallel to [001] hosting TlS6 and (As5Sb)S3 disymmetric polyhedra. Ralphcannonite is derived from its isotype routhierite M1iCuM2Hg2TlAs2S6 through the double heterovalent substitution M1Cu+ + M2Hg2+→ M1Zn2+ + M2Ag+. This substitution obeys a steric constraint, with Ag+, the largest cation relative to Zn2+ and Cu+, entering the largest Ml site, as observed in arsiccioite. The ideal crystal-chemical formula of ralphcannonite is M1ZmM2(Zn0.5Ag0.5)2TlAs2S6.