Homologous silver bismuth chalcogenide halides (N, x)P. II. The (2, x)P and (3, x)P structure families of modular compounds with tunable composition and structure

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Beitragende

Abstract

The crystal structures of two members of the solid solution series Ag 3xBi5-3xS8-6xCl6x-1 (x = 0.52 (I), x = 0.67 (II)) and three compounds of the Ag4xBi6-4xQ 10-8xBr8x-2 series (Q = S: x = 0.70 (III), x = 0.84 (IV); Q = Se: x = 0.72 (V)) were determined by single-crystal X-ray diffraction. The compounds crystallize in the monoclinic space group C2/m (No. 12) with a = 1326.7(3), b = 403.9(1), c = 1176.7(2) pm, β = 107.83(3)° for (I); a = 1325.4(3), b = 403.3(1), c = 1170.6(2) pm, β = 108.14(3)° for (II); a = 1338.9(4), b = 407.7(1), c = 1426.4(4) pm, β = 113.95(2)° for (III); a = 1346.7(4), b = 409.3(1), c = 1440.7(4) pm, β = 114.40(1)° for (IV); and a = 1370.9(2), b = 417.64(4), c = 1480.4(2) pm, β = 114.92(2)° for (V). (I) and (II) adopt the PbBi4S7 structure type, (III) to (V) crystallize in the CuBi5S8 type. All five compounds belong to the homologous series with general formula [BiQX]2[Ag xBi1-xQ2-2xX2x-1]N+1 (Q = S, Se; X = Cl, Br; 1/2 ≤ x ≤ 1)), which resemble minerals of the pavonite series. They are characterized by the parameters N and x and are denoted (N, x)P. In the crystal structures, two kinds of layered modules alternate along [001]. Modules of type A uniformly consist of paired rods of face-sharing monocapped trigonal prisms around Bi atoms with octahedra around mixed occupied metal positions (M = Ag/Bi) between them. Modules of type B are composed of chains of edge-sharing [MZ6] octahedra (M = Ag/Bi; Z = Q/X). These NaCl-type fragments are of thickness N = 2 in Ag3xBi 5-3xS8-6xCl6x-1 and N = 3 in Ag 4xBi6-4xQ10-8xBr8x-2. All structures exhibit Ag/Bi disorder in octahedrally coordinated metal positions and Q/X mixed occupation of some anion positions.

Details

OriginalspracheEnglisch
Seiten (von - bis)475-481
Seitenumfang7
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang634
Ausgabenummer3
PublikationsstatusVeröffentlicht - März 2008
Peer-Review-StatusJa

Externe IDs

ORCID /0000-0002-2391-6025/work/159171934

Schlagworte

ASJC Scopus Sachgebiete

Schlagwörter

  • Bismuth, Chalcogenides, Halides, Pavonite, Silver, Solid solutions