Crystal structures of the high temperature forms of V{sub 8}O{sub 15} and V{sub 9}O{sub 17} and structural trends in the V{sub n}O{sub 2n-1} Magneli series

Journal Article · Fri Feb 15 04:00:00 EST 2013 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2012.09.030· OSTI ID:22149992

Cava, R. J. ^[1]

---

1. Department of Chemistry, Princeton University, Princeton, NJ 08544 (United States)

We report the structure of the metallic high-temperature (ht) form of V{sub 9}O{sub 17}, determined from single crystal X-ray diffraction: space group=P-1 a=5.4219(7) A, b=7.0142(9) A, c=14.5252(19) A, {alpha}=97.0310(10) Degree-Sign , {beta}=90.9900(10) Degree-Sign , {gamma}=108.9630(10) Degree-Sign , V=517.53(12) A{sup 3}, and Z=2. We also report refinement of the structure of metallic ht-V{sub 8}O{sub 15}, space group=P-1, a=5.4315(17) A, b=7.015(2) A, c=13.147(5) A, {alpha}=100.144(4) Degree-Sign , {beta}=95.776(4) Degree-Sign , {gamma}=108.965(3) Degree-Sign , V=459.6(3) A{sup 3}, and Z=2. The structure of metallic V{sub 9}O{sub 17} is interpreted and discussed in the context of the V{sub n}O{sub 2n-1} Magneli phases, yielding trends about how the underlying forces contribute to the metal to insulator transition (MIT). The manner in which structural features of the metallic phases change as a function of n supports previous arguments that there is a turnover in the forces leading to the MIT between n=6 and n=8. - Graphical abstract: Left: The crystal structures of V{sub 8}O{sub 15} and V{sub 9}O{sub 17} shown in context of the crystallographic shear family V{sub n}O{sub 2n-1}. Right: The lattice parameters of V{sub n}O{sub 2n-1} as a function of n. The anamolous trend in b exhibits similar behavior as the metal to insulator (MIT) transition temperature (red). Highlights: Black-Right-Pointing-Pointer Crystal structures of the metallic forms of V{sub 8}O{sub 15} and V{sub 9}O{sub 17}. Black-Right-Pointing-Pointer General trends across the V{sub n}O{sub 2n-1} allow designation of two chain types in all phases. Black-Right-Pointing-Pointer Triclinic b lattice parameter varies anomalously with n, in V{sub n}O{sub 2n-1}. Black-Right-Pointing-Pointer Trend in b matches the metal to insulator transition temperature trend.

• OSTI ID: 22149992
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. 198; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
CRYSTAL STRUCTURE
CRYSTALLOGRAPHY
LATTICE PARAMETERS
MONOCRYSTALS
SPACE GROUPS
TEMPERATURE RANGE 0400-1000 K
TRANSITION TEMPERATURE
X-RAY DIFFRACTION