(Mn1−xPbx)Pb10+ySb12−yS26−yCl4+yO, a new oxy-chloro-sulfide with ∼2 nm-spaced (Mn,Pb)Cl4 single chains within a waffle-type crystal structure

The new oxy-chloro-sulfide (Mn1−xPbx)Pb10+ySb12−yS26−yCl4+yO (x ∈ [0.2–0.3]; y ∈ [0.3–1.6]) was synthesized by dry way at 500–600 °C. A single crystal ∼Mn0.7Pb11.0Sb11.3S25.3Cl4.7O indicates a monoclinic symmetry, space group C2/m, with a = 37.480(8), b = 4.1178(8), c = 18.167(4) Å, β = 106.37(3)°, V = 2690.2(9) Å3, Z = 2. Its crystal structure was determined by X-ray single crystal diffraction, with a final R = 5.11%. Modular analysis of the crystal structure reveals a “waffle” architecture, where complex rods with lozenge section delimitate an internal channel filled by a single chain of (Mn0.7Pb0.3)Cl6 octahedra connected by opposite edges. Minimal inter-chain distances are close to 18 Å. The rod wall, two-atom thick, presents, in alternation with S atoms, Pb or (Pb,Sb) cations with prismatic coordination in the internal atom layer, while the external atom layer is constituted exclusively by Sb cations with dissymmetric square pyramidal coordination. A (Pb,Sb)2S2 fragment connects two successive rods along (2 0 1) to form a waffle-type palissadic layer. The unique O position, half filled, presents the same environment than the isolated O positions in the oxy-sulfide Pb14Sb30S54O5, or oxy-chloro-sulfides Pb18Sb20S46Cl2O and (Cu,Ag)2Pb21Sb23S55ClO. This compound belongs to a pseudo-homologous series of chalcogenides with waffle structure, ordered according to the size of their lozenge shape channel. Such a complex senary compound of the oxy-chloro-sulfide type illustrates the structural competition between three cations, on one hand, and, on the other hand, three anions. This compound is of special interest regarding the 1D distribution of magnetic Mn2+ atoms at the ∼2 nm scale.

Projection of the crystal structure of (Mn1-xPbx)Pb10+ySb12-yS26-yCl4+yO restricted to two adjacent rods, showing the minimum distance between (Mn, Pb)Cl4 single chains.Figure optionsDownload as PowerPoint slide