Lead-antimony sulfosalts from Tuscany (Italy); VII, Crystal structure of pellouxite, approximately (Cu,Ag) (sub 2) Pb (sub 21) Sb (sub 23) S (sub 55) ClO, an expanded monoclinic derivative of Ba (sub 12) Bi (sub 24) S (sub 48) hexagonal sub-type (zinkenite group)

The crystal structure of pellouxite, a natural Pb-Sb-(Cu, Ag) oxy-chloro-sulfide from Tuscany (Italy), has been solved and refined using single-crystal X-ray-diffraction, with a final R = 0.044. The symmetry is monoclinic, space group C 2/m, with a = 55.824(11), b = 4.0892(8), c = 24.128(5) A, beta = 113.14(3) degrees , V = 5065(2) A (super 3) . The structural formula is close to (Cu (sub 0.68) Ag (sub 0.26) )Pb (sub 10.44) Sb (sub 11.56) S (sub 27) (Cl (sub 0.5) S (sub 0.5) )O (sub 0.5) , with Z = 4, or, ideally (according to ordering revealed by a weak 2b superstructure), (Cu,Ag) (sub 2) Pb (sub 21) Sb (sub 23) S (sub 55) ClO, with Z = 4. Among cations, there are 9 pure Pb positions, 10 pure Sb positions, and 3 Pb/Sb and one Cu/Ag pairs. Together with 27 S atoms, there are one Cl/S pair, as well as one isolated half-filled O position. All the minor elements (Cu with Ag, Cl and O) appear essential for the organization of the crystal structure. The Cu/Ag pair is located within a triangular bipyramid (four S and one Cl/S); vacancies on this site (fixed to 0.06 %) have been correlated to an equivalent Sb excess in the neighbouring Pb/Sb pair according to the substitution Pb (super 2+) + (Cu, Ag) (super +) --> Sb (super 3+) + vacancy. The isolated oxygen is strongly bonded to two Sb atoms, like in scainiite and pillaite. The Cl/S pair is situated in a triangular prismatic coordination (4 Pb + 2 Sb). Following the principles of modular analysis, the whole structure is described in two ways: 1 - a combination of three types of 1D and 2D building blocks, each of them organized around Sb 3+ lone-electron-pair micelles, or 2 - a single type of complex rod-layer parallel to (20 Gamma ), organized around columns with pseudo-trigonal symmetry. Pellouxite constitutes the second example of oxy-chloro-sulfosalt after pillaite. It is an expanded monoclinic derivative of synthetic hexagonal Ba (sub 12) Bi (sub 24) S (sub 48) , structurally related to scainiite, Pb (sub 14) Sb (sub 30) S (sub 54) O (sub 5) (topological similarity for about 90 % of the atom positions). It belongs to the zinkenite group of cyclically twinned sulfosalt structures and derivatives.