Quick Search:    advanced search

GSW Home   GeoRef Home   My GSW Alerts   Contact GSW   About GSW   Journals List   Help

This Article Abstract Résumé Full Text Full Text (PDF) Alert me when this article is cited Alert me if a correction is posted Citation Map Services Email this article to a friend Similar articles in this journal Alert me to new issues of the journal Download to citation manager Citing Articles Citing Articles via Google Scholar Google Scholar Articles by Makovicky, E. Articles by Topa, D. Search for Related Content

THE CRYSTAL STRUCTURE OF SULFOSALTS WITH THE BOXWORK ARCHITECTURE AND THEIR NEW REPRESENTATIVE, Pb_15–2xSb_14+2xS₃₆O_x

Emil Makovicky^1, and Dan Topa²

¹ Department of Geography and Geology, University of Copenhagen, Østervoldgade 10, DK–1350 Copenhagen, Denmark
² Department of Material Research & Physics, University of Salzburg, Hellbrunnerstrasse 34, A–5020 Salzburg, Austria

View larger version (56K): [in this window] [in a new window]   FIG. 1. Labeling of cations and anions in one asymmetric unit of the crystal structure of Pb15–2xSb14+2xS36Ox. Note the oxygen position below Sb14.

View larger version (118K): [in this window] [in a new window]   FIG. 2. The crystal structure of Pb15–2xSb14+2xS36Ox. Here and in the remaining figures, Pb is dark blue, Sb red, Hg, Ag or Mn (where applicable) are green, S and Bi are colorless, O is light blue, and Cl is yellow. Two kinds of rods forming walls (vertical in the figure) and their lone-electron-pair micelles (lighter, along median planes), and those forming partitions (horizontal) and boxwork fill, respectively, are delineated by increasingly dark shading. Non-commensurate interspaces between rods are left unshaded. Note the (capped) standing and lying-down trigonal coordination prisms of Pb.

View larger version (103K): [in this window] [in a new window]   FIG. 3. The crystal structure of scainiite (Moëlo et al. 2000) with a high concentration of "kermesite-like configurations" along (001) planes, in continuation of "horizontal" interspaces. Oxygen is shown in light blue.

View larger version (125K): [in this window] [in a new window]   FIG. 4. The crystal structure of marrucciite (Orlandi et al. 2007) Note the two distinct flat-octahedron Hg sites in the vertical walls; it was left unshaded.

View larger version (91K): [in this window] [in a new window]   FIG. 5. The crystal structure of pillaite (Meerschaut et al. 2001). For conventions, see Figure 2. Rods of the walls (vertical) are terminated by "kermesite-like configurations", and box-fill rods are completed by chlorine atoms (yellow).

View larger version (126K): [in this window] [in a new window]   FIG. 6. The crystal structure of pellouxite (Palvadeau et al. 2004). Note the two distinct ways in which rods in the walls are terminated: by SbS5 pyramids and by "kermesitelike" configurations, respectively. The latter allow deep insertion of rods forming horizontal partitions into the spaces created.

View larger version (100K): [in this window] [in a new window]   FIG. 7. The crystal structure of the synthetic Mn–Pb oxychlorosulfosalt (Doussier et al. 2007). Note the "kermesite-like configurations" in the walls and single-octahedron columns of (Mn,Pb)Cl4 stoichiometry in the box interior.

View larger version (112K): [in this window] [in a new window]   FIG. 8. The crystal structure of neyite (Makovicky et al. 2001). The Ag atom in the walls has a linear coordination, whereas Cu has tetrahedral and triangular coordination, respectively. Partitions (grey) and box-fill (dark grey) underwent crystallographic shear midway between walls.

View larger version (96K): [in this window] [in a new window]   FIG. 9. Rod configurations common to Pb15–2xSb14+2xS36Ox (left) and pellouxite (right). Note the mutual shifts in the heights of rods by 2 Å, when proceeding along either crystallographic direction. They are different in the two phases and are expressed by coloring of atoms (light and dark). Note also the additional structure portions present in Pb15–2xSb14+2xS36Ox.

View larger version (80K): [in this window] [in a new window]   FIG. 10. Two distinct "kermesite-like configurations" in the crystal structure of scainiite. In the order of decreasing size, spheres indicate S, Pb, Sb, and O. The Sb–S, Pb–S and Sb–O bonds are indicated, the long Sb–S bonds (interactions) are shown using a smaller diameter. Chains are parallel to [010]. Modified from Moëlo et al.(2000).

View larger version (119K): [in this window] [in a new window]   FIG. 11. The crystal structure of vurroite (Pinto et al. 2008). Two kinds of walls, respectively composed of rods, two and three pyramids wide (indicated by two kinds of shading), enclose boxes with a single-octahedron (Sn, Bi) fill.

View larger version (125K): [in this window] [in a new window]   FIG. 12. The crystal structure of rouxelite (Orlandi et al. 2005). Note the flattened octahedron of Hg and the tetrahedrally coordinated Cu atoms. There are three kinds of modules, which lead to a local but not a global kinship to the kobellite structure-type. Details are in the text.

View larger version (96K): [in this window] [in a new window]   FIG. 13. The crystal structure of Bi2In4S9 (Chapuis et al. 1972) with six- and five-coordinated indium, and square-pyramidal Bi. Three kinds of elements are present: "porous" walls (vertical), partitions and double-octahedron chains as a fill.

View larger version (106K): [in this window] [in a new window]   FIG. 14. The crystal structure of the synthetic Pb–La–Bi sulfosalt (Iordanidis & Kanatzidis 2001). The boxwork consists of two-sheet-thick pseudotetragonal walls with no obvious division into walls and partitions, and a seven-coordinated cation in wall intersections.

View larger version (102K): [in this window] [in a new window]   FIG. 15. The crystal structure of Er9La10S27 (Carré & Laruelle 1973). Walls underwent a homologous expansion in comparison to those in Figure 14, partitions have greater length, and the filling elements are three-strand ribbons of octahedra. A conspicuous configurational affinity exists to the sulfosalt structure in Figure 14.

View larger version (116K): [in this window] [in a new window]   FIG. 16. The crystal structure of CeTmS3 (Rodier 1973). It has complex walls (see text), simple partitions, and octahedron elements of the boxfill similar to, but narrower than, those in Figure 14. Cerium prefers a bicapped trigonal prismatic coordination, whereas Tm prefers coordination by six and seven ligands.