Novel chain and oligomeric condensed cluster phases for gadolinium iodides with manganese interstitials
- Iowa State Univ., Ames, IA (United States)
Reactions in the Gd-I-Mn system near 800{degree}C in sealed Nb containers provide good yields of Gd{sub 3}I{sub 3}Mn and Gd{sub 5}I{sub 7}Mn. The first is isostructural with the Pr{sub 3}I{sub 3}Ru family (P2{sub 1}/m, Z = 2, a = 8.928(3) {Angstrom}, b = 4.127(1) {Angstrom}, c = 12.266(4) {Angstrom}, {beta} = 05.51(2){sup o}; R,R {sub w} = 3.5, 3.4%). both structures exhibit substantially shorter Mn-Mn interactions than seen before with electron-richer interstitials. Distorted double chains of edge-sharing Gd{sub 6}Mn octahedra in Gd{sub 3}I{sub 3}Mn resemble those in Y{sub 3}I{sub 3}(Ru,Ir), but with 2.66-{Angstrom} separations in a distinct zigzag Mn chain within. The new Gd{sub 5}I{sub 7}Mn contains two types of clusters: (a) Gd{sub 16}I{sub 20}Mn{sub 4} units that closely resemble the Ru{sub 4}-centered tetracapped truncated tetrahedron Y{sub 16} in Y{sub 16}Ru{sub 4} but with strong Mn displacements to d(Mn-Mn) = 2.825 {Angstrom} in the centered tetrahedra; (b) Gd{sub 4}I{sub 8} capped tetrahedra interbonded with those of type a which have {approximately}25% of each metal vertex displaced outward in a disordered manner. The small type b clusters appear to be oxidized to give a (Gd{sub 4}I{sub 8}){sup 4+}[Gd{sub 16}(Mn){sub 4}I{sub 20}]{sup 4{minus}} formulation. Calculations suggest this arrangement does not give a closed configuration with these elements, perhaps because of the stochiometry limitations with a single type of interstitial.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 450852
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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