(Mn{sub 1-x}Pb{sub x})Pb{sub 10+y}Sb{sub 12-y}S{sub 26-y}Cl{sub 4+y}O, a new oxy-chloro-sulfide with {approx}2 nm-spaced (Mn,Pb)Cl{sub 4} single chains within a waffle-type crystal structure
- Institut des Materiaux Jean Rouxel, UMR 6502 CNRS-Universite de Nantes, 2 rue de la Houssiniere, BP 32229, 44322 Nantes cedex 03 (France)
The new oxy-chloro-sulfide (Mn{sub 1-x}Pb{sub x})Pb{sub 10+y}Sb{sub 12-y}S{sub 26-y}Cl{sub 4+y}O (x element of [0.2-0.3]; y element of [0.3-1.6]) was synthesized by dry way at 500-600 deg. C. A single crystal {approx}Mn{sub 0.7}Pb{sub 11.0}Sb{sub 11.3}S{sub 25.3}Cl{sub 4.7}O indicates a monoclinic symmetry, space group C2/m, with a = 37.480(8), b 4.1178(8), c = 18.167(4) A, {beta} = 106.37(3){sup o}, V = 2690.2(9) A{sup 3}, 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 (Mn{sub 0.7}Pb{sub 0.3})Cl{sub 6} octahedra connected by opposite edges. Minimal inter-chain distances are close to 18 A. 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){sub 2}S{sub 2} 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 Pb{sub 14}Sb{sub 30}S{sub 54}O{sub 5}, or oxy-chloro-sulfides Pb{sub 18}Sb{sub 20}S{sub 46}Cl{sub 2}O and (Cu,Ag){sub 2}Pb{sub 21}Sb{sub 23}S{sub 55}ClO. 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 Mn{sup 2+} atoms at the {approx}2 nm scale. - Graphical abstract: Projection of the crystal structure of (Mn{sub 1-x}Pb{sub x})Pb{sub 10+y}Sb{sub 12-y}S{sub 26-y}Cl{sub 4+y}O restricted to two adjacent rods, showing the minimum distance between (Mn, Pb)Cl{sub 4} single chains.
- OSTI ID:
- 21043811
- Journal Information:
- Journal of Solid State Chemistry, Vol. 180, Issue 8; Other Information: DOI: 10.1016/j.jssc.2007.05.012; PII: S0022-4596(07)00189-2; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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