Watanabeite from the Pefka epithermal deposit, northeastern Greece, was examined using single-crystal X-ray diffraction and electron microprobe analysis. The empirical formula of watanabeite is Cu3.93Fe0.10Ag0.01Pb0.23As1.55Sb0.19S4.99. This mineral is orthorhombic, space group Amm2, with unit-cell parameters a = 10.9601(5), b = 14.6498(8), c = 10.3001(5) Å, V = 1653.82(14) Å3 and Z = 8. The crystal structure was solved and refined to R1 = 0.0471 for 2108 unique reflections with Fo > 4σ(Fo) and 123 refined parameters. The crystal structure of watanabeite can be described as a three-dimensional framework of Cu-centred tetrahedra; cavities of the tetrahedral scaffolding host Cu6S and As2(Pb,Sb,As)2S7 clusters. On the basis of structural data, the formula of watanabeite could be written as [III]Cu3[IV]Cu5As3(Pb,Sb,As)S10 (Z = 4), considering the three independent three-fold Cu sites and the three independent tetrahedrally coordinated Cu sites as aggregated positions. The occurrence of Pb2+ in watanabeite is probably related to the substitution Cu+ + (As,Sb)3+ = 2Me2+, where Me = Pb, Fe, Zn and formally divalent Cu. The relationships with tetrahedrite-group minerals are discussed on the basis of the refined structural model, highlighting possible crystal chemical implications of such relationships.

Watanabeite Cu4(As,Sb)2S5, in which As>Sb, is a new copper sulphosalt that occurs with quartz in a hydrothermal vein at the Teine mine, Sapporo, Hokkaido, Japan. It is silvery lead-grey in colour with lead-grey streak. VHN100 = 253-306 kg/mm2, brittle. It has no cleavage and the fracture is uneven. The measured density = 4.66(2) g/cm3. The mean of six microprobe analyses gave Cu 41.1, Ag 0.1, Mn 0.3, As 15.4, Sb 14.3, Bi 2.4, S 26.2, a total of 99.8 wt.%, corresponding to: (Cu3.94Mn0.03− Ag0.01)∑3.98(As1.25Sb0.72Bi0.07)∑2.04S4.98 (basis: total atoms = 11), or ideally, Cu4(As,Sb)2S5, with As > Sb. The X-ray powder pattern resembles that of tetrahedrite but has subsidiary diffractions and is similar to that of synthetic Cu24As12S31 (Maske and Skinner, 1971). It is indexed on an orthorhombic cell with a = 14.51 Å, b = 13.30 Å, c = 17.96 Å (all ± 0.01 Å), and Z = 16. Calculated density is 4.66 g/ cm3. It is optically similar to tetrahedrite but is grey and weakly bireflectant. No internal reflections were observed. The maximum and minimum reflectance values in air and in oil (nD = 1.515) for the COM wavelengths are: 470 nm −32.5, 31.5; 17.7, 17.0, 546 nm −32.0, 31.1; 17.0, 16.3,589 nm −31.1, 30.3; 16.1 m 15.5, 650 nm −30.0, 29.3; 15.0, 14.5%, respectively. Watanabeite forms masses composed of aggregates of minute grains up to 50 μm in diameter. Apart from some minute inclusions of emplectite, native bismuth and tennantite, it is almost monominerallic.