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La[sub 5]Mo[sub 4]O[sub 16]: A new structural type related to perovskite with extremely short Mo-Mo bonds

Journal Article · · Journal of Solid State Chemistry; (United States)
; ; ;  [1];  [2]
  1. Laboratoire CRISMAT, Caen (France)
  2. Rider College, Lawrenceville, NJ (United States)

The structure of La[sub 5]Mo[sub 4]O[sub 16] has been determined using single crystal X-ray diffraction methods. Samples, prepared by fused salt electrolysis, were found to crystallize with monoclinic symmetry, space group C2/m, a = 7.9638(7), b = 7.9958(5), c = 10.3345(7) [angstrom], [beta] = 95.067(6)[degrees]. Atomic parameters were refined to R = 0.031 and R[sub w] = 0.034. The structure is closely related to that of perovskite, with ReO[sub 3]-like layers parallel to (001) containing two types of MoO[sub 6] octahedra. These layers are connected to each other through Mo[sub 2]O[sub 10] units, formed by two edge-sharing MoO[sub 6] octahedra. In these units, an exceptionally short Mo-Mo distance (2.406 [angstrom]) is observed. The separation of perovskite-like layers by Mo[sub 2]O[sub 10] units may impart quasi-low-dimensional electronic properties to this mixed valence phase. The valence of the three independent molybdenum atoms is discussed. Lanthanum atoms are located in two different cages: La(1) is at the center of an incomplete perovskite cage with 12 oxygen atoms as nearest neighbors, while La(2) is in a cage bounded by four Mo[sub 2]O[sub 10] units with a distorted cubic coordination. Two of the oxygen atoms were found to be crystallographically disordered, yielding a local triclinic symmetry which through averaging becomes monoclinic. 9 refs., 3 figs., 3 tabs.

OSTI ID:
5726896
Journal Information:
Journal of Solid State Chemistry; (United States), Journal Name: Journal of Solid State Chemistry; (United States) Vol. 105:1; ISSN 0022-4596; ISSN JSSCBI
Country of Publication:
United States
Language:
English