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The new silver(I)thioantimonate(III) [C{sub 4}N{sub 2}H{sub 14}][Ag{sub 3}Sb{sub 3}S{sub 7}] and a new structural variant of the silver(I)thioantimonate(III) [C{sub 2}N{sub 2}H{sub 9}]{sub 2}[Ag{sub 5}Sb{sub 3}S{sub 8}] both synthesized under solvothermal conditions

Journal Article · · Journal of Solid State Chemistry
 [1];  [1];  [1]
  1. Institut fuer Anorganische Chemie, Christian-Albrechts-Universitaet Kiel, Olshausenstr. 40, D-24098 Kiel (Germany)
The novel silver(I)thioantimonates(III) [C{sub 4}N{sub 2}H{sub 14}][Ag{sub 3}Sb{sub 3}S{sub 7}] (I) (C{sub 4}N{sub 2}H{sub 12}=1,4-diaminobutane) and [C{sub 2}N{sub 2}H{sub 9}]{sub 2}[Ag{sub 5}Sb{sub 3}S{sub 8}] (II) (C{sub 2}N{sub 2}H{sub 8}=ethylenediamine) were synthesized under solvothermal conditions using AgNO{sub 3}, Sb, S and the amines as structure directing molecules. Both compounds crystallize as orange needles with lattice parameters a=6.669(1) A, b=30.440(3) A, c=9.154(1) A for I (space group Pnma), and a=6.2712(4) A, b=15.901(1) A, c=23.012(2) A, {beta}=95.37(1){sup o} for II (space group P2{sub 1}/n). In both compounds the primary building units are trigonal SbS{sub 3} pyramids, AgS{sub 3} triangles and AgS{sub 4} tetrahedra. In I the layered [Ag{sub 3}Sb{sub 3}S{sub 7}]{sup 2-} anion is constructed by two different chains. An [Sb{sub 2}S{sub 4}] chain running along [100] is formed by vertex sharing of SbS{sub 3} pyramids. The second chain contains a Ag{sub 3}SbS{sub 5} group composed of the AgS{sub 4} tetrahedron, two AgS{sub 3} units and one SbS{sub 3} pyramid. The Ag{sub 3}SbS{sub 5} units are joined via S atoms to form the second chain which is also directed along [100]. The layered anion is then obtained by condensation of the two individual chains. The organic structure director is sandwiched by the inorganic layers and the shortest inter-layer distance is about 6.4 A. In II the primary building units are linked into different six-membered rings which form a honeycomb-like layer. Two such layers are connected via Ag-S bonds of the AgS{sub 4} tetrahedra giving the final undulated double layer anion. The structure directing ethylenediamine cations are located in pairs between the layers and a sandwich-like arrangement of alternating anionic layers and organic cations is observed. The inter-layer separation is about 5.4 A. Both compounds decompose in a more or less complex manner when heated in an argon atmosphere. The optical band gaps of about 1.9 eV for the two compounds proof the semiconducting behavior. For II the conductivity was measured with impedance spectroscopy and amounts to {sigma} {sub 295K}=7.6x10{sup -7} {omega}{sup -1} cm{sup -1}. At 80 deg. C the conductivity is significantly larger by one order of magnitude. - Graphical abstract: In the new silver thioantimonate, [C{sub 4}N{sub 2}H{sub 14}][Ag{sub 3}Sb{sub 3}S{sub 7}], the layered [Ag{sub 3}Sb{sub 3}S{sub 7}]{sup 2-} anion is constructed by two different chains. An [Sb{sub 2}S{sub 4}] chain is formed by vertex sharing of SbS{sub 3} pyramids. The second chain contains Ag{sub 3}SbS{sub 5} group which are connected by S atoms. The layered anion is obtained by condensation of the two individual chains. The organic structure director is sandwiched by the inorganic layers and the shortest inter-layer distance is about 6.4 A.
OSTI ID:
20902480
Journal Information:
Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 11 Vol. 179; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English