Some reduced ternary and quaternary oxides of molybdenum. A family of compounds with strong metal-metal bonds

Journal Article · Fri May 01 04:00:00 EDT 1981 · J. Solid State Chem.; (United States)

DOI:https://doi.org/10.1016/0022-4596(81)90502-8· OSTI ID:6455854

Torardi, C C; McCarley, R E

Several new, reduced ternary and quaternary oxides of molybdenum are reported, each containing molybdenum in an average oxidation state < 4.0. All are prepared by reactions between a molybdate salt; metal oxide, if needed; and MoO/sub 2/ sealed in Mo tubes held at 1100/sup 0/C for ca. 7 days. Refinement of the substructure of the new compound Ba/sub 0/ /sub 62/Mo/sub 4/O/sub 6/ was based on an orthorhombic cells, with a = 9.509(2), b = 9.825(2), c = 2.853(1) A, Z = 2 in space group Pbam; weak supercell reflections indicate the true structure has c = 8(2.853) A. The chief structural feature is closely related to that of NaMo/sub 4/O/sub 6/ which consists of infinite chains of Mo/sub 6/ octahedral clusters fused on opposite edges, bridged on the outer edges by O atoms and crosslinked by Mo-O-Mo bonding to create four-sided tunnels in which the Ba/sup 2 +/ ions are located. The structure of Ba/sub 1/ /sub 13/Mo/sub 8/O/sub 16/ is triclinic, a = 7.311(1), b = 7.453(1), c = 5.726(1) A, ..cap alpha.. = 101.49(2), ..beta.. = 99.60(2), ..gamma.. = 89.31(2)/sup 0/, Z = 1, space group P1. It is a low-symmetry, metal-metal bonded variant of the hollandite structure, in which two different infinite chains, built up from Mo/sub 4/O/sub 8//sup 2 -/ and Mo/sub 4/O/sub 8//sup 0/ /sup 26 -/ cluster units, respectively, are interlinked via Mo-O-Mo bridge bonding to create again four-sided tunnels in which the Ba/sup 2 +/ ions reside. Other compounds prepared and characterized by analyses and x-ray powder diffraction data are Pb/sub x/Mo/sub 4/O/sub 6/ (x approx. 0.6), LiZn/sub 2/Mo/sub 3/O/sub 8/, , CaMo/sub 5/O/sub 8/, K/sub 2/Mo/sub 12/O/sub 19/, and Na/sub 2/Mo/sub 12/O/sub 19/.

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6455854
• Journal Information: J. Solid State Chem.; (United States), Journal Name: J. Solid State Chem.; (United States) Vol. 37:3; ISSN JSSCB
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKALINE EARTH METAL COMPOUNDS
BARIUM COMPOUNDS
CALCIUM COMPOUNDS
CHALCOGENIDES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
LEAD COMPOUNDS
LITHIUM COMPOUNDS
MOLYBDATES
MOLYBDENUM COMPOUNDS
MOLYBDENUM OXIDES
OXIDES
OXYGEN COMPOUNDS
POTASSIUM COMPOUNDS
SODIUM COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
ZINC COMPOUNDS