The crystal structure of the rare mineral dalnegroite, Tl5–xPb2x(As,Sb)21–xS34 with x ≈ 1, was determined for a crystal from Lengenbach, Binn Valley, Switzerland. The structure is triclinic, space group P1, with a = 16.218(3), b = 42.546(7), c = 8.558(1) Å, α = 95.70(4), β = 90.18(3), γ = 96.38(4)°, V = 5838.9(9) Å3, Z = 4. Refinement of an isotropic model led to an R1 index of 0.0536 for 22226 observed reflections and 980 parameters, and R1 = 0.0590 for all 25266 independent reflections. Although dalnegroite cannot be considered a layered compound, its structure can be usefully described as a regular alternation of two kinds of layers stacked along the b axis, with four layers in the unit cell: (1) a layer 7.8 Å thick, at y ≈ 0.15 and 0.65, can be considered as derived from the SnS archetype; (2) a layer 13.6 Å thick, at y ≈ 0.35 and 0.85, derived from the PbS archetype. Different chemical compositions, such as Tl:Pb and Sb:As ratios, for different samples belonging to the chabournéite-dalnegroite family could play a central role in controlling different degrees of order, leading to different superstructures.

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