Oxybismuthides

Oxybismuthides or bismuthide oxides are chemical compounds formally containing the group BiO, with one bismuth and one oxygen atom. The bismuth and oxygen are not bound together as in bismuthates, instead they make a separate presence bound to the cations (metals), and could be considered as a mixed bismuthide-oxide compound. So a compound with OmBin requires cations to balance a negative charge of 2m+3n. The cations will have charges of +2 or +3. The trications are often rare earth elements or actinides. They are in the category of oxypnictide compounds.

Many of the bismuthide oxides have bismuth in an unusual -2 oxidation state. The ones with Ln2BiO2 have the anti-ThCr2Si2 structure. They include alternating layers of LnO (anti-fluorite-type) and LnBiO. The Eu4Bi2O has an anti-K2NiF4 structure, the same as for Na2Ti2As2O. Some other compounds contain calcium and a rare earth CaRE3BiO4, and Ca2RE8Bi3O10.[1]

Some of these compounds are superconductors at very low temperatures and many are semiconductors at standard conditions.[1]

Examples
formula name mw structure space group cell appearance properties supercondicting Tc reference
LaNiBiO Lanthanum nickel oxybismuthide 4.2 [2]
Cm2BiO2 tetragonal I4/mmmm a=3.957 c=13.359 [3]
Am2BiO2 Americium dioxybismuthide orthorhombic Pnam a=5.053 b=8.092 c=5.738 [4]
BaTi2Bi2O tetragonal a = 4.046 Å, c = 7.272 Å [5]
Ti8BiO7 octatitanium bismuthide heptoxide orthorhombic Cmmm I = 7.8473 Å, b = 16.829 Å, c = 3.0256 Å silver conductor [6]
Nd2BiO2 529.46 tetragonal I4/mmm a=399.11 c = 1366.3 V=217.53 dark grey [7]
Tb2BiO2 558.82 tetragonal I4/mmm a=389.62 c=1331.7 V=202.16 dark grey [7]
Dy2BiO2 565.98 tetragonal I4/mmm a=387.61 c=1323.3 V=198.82 dark grey [7]
Ho2BiO2 570.84 tetragonal I4/mmm a=385.83 c=1321.8 V=196.77 dark grey [7]
La2BiO2 I4/mmm a=4.08083 c=13.9866 V=198.74 [8]
Er2BiO2 I4/mmm a=3.84531 c=13.1513 V=194.48 [8]
Gd2BiO2 I4/mmm a=3.9181 c=13.4246 V=206.09 [9]
Y2BiO2 I4/mmm a=3.8734 c=13.2469 V=198.74 [9]
Pr2BiO2 I4/mmm [9]
Nd2BiO2 I4/mmm a=3.99258 c=13.6663 V=217.851 [9]
Ho2BiO2 I4/mmm a=3.86212 c=13.2262 V=197.28 [9]
Sm2BiO2 I4/mmm a=3.95296 c=13.5083 V=211.074 [9]
Ce2O2Bi I4/mmm a=4.034 c=13.736 [1][10]
Sm4Bi2O [11]
Eu4Bi2O [1]
Ba2Cd2.13Bi3O Dibarium tricadmium bismuthide(-I,-III) oxide tetragonal I4/mmm a = 4.7396 c = 43.601 V=979.5 Z=4 black [12]
Gd3BiO3 monoclinic C2/m [13]
Gd8Bi3O8 monoclinic C2/m grey [13]
Ca2RE7Bi5O5 grey [1]
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References
  1. Forbes, Scott; Mozharivskyj, Yurij (2017-11-28). "Rare-Earth Pnictide Oxides ( RE ,Ca) m Pn n O m ( Pn = Sb, Bi): A Review of Crystal Structures, Chemistry, Compositions, and Physical Properties". Chemistry of Materials. 29 (22): 9605–9612. doi:10.1021/acs.chemmater.7b03996. ISSN 0897-4756.
  2. Kozhevnikov, V. L.; Leonidova, O. N.; Ivanovskii, A. L.; Shein, I. R.; Goshchitskii, B. N.; Kar’kin, A. E. (5 February 2009). "New superconductor with a layered crystal structure: Nickel oxybismuthide LaO1−δNiBi". JETP Letters. 87 (11): 649–651. doi:10.1134/S002136400811012X.
  3. Seaborg, G. T.; Katz, Joseph J.; Morss, L. R. (2012). The Chemistry of the Actinide Elements. Springer Science & Business Media. p. 972. ISBN 978-94-009-3155-8.
  4. Seaborg, G. T.; Katz, Joseph J.; Morss, L. R. (2012). The Chemistry of the Actinide Elements. Springer Science & Business Media. p. 902. ISBN 978-94-009-3155-8.
  5. Hosono, Hideo; Tanabe, Keiichi; Takayama-Muromachi, Eiji; Kageyama, Hiroshi; Yamanaka, Shoji; Kumakura, Hiroaki; Nohara, Minoru; Hiramatsu, Hidenori; Fujitsu, Satoru (2015-05-08). "Exploration of new superconductors and functional materials, and fabrication of superconducting tapes and wires of iron pnictides". Science and Technology of Advanced Materials. 16 (3): 033503. arXiv:1505.02240. Bibcode:2015STAdM..16c3503H. doi:10.1088/1468-6996/16/3/033503. ISSN 1468-6996. PMC 5099821. PMID 27877784.
  6. Amano, Shinsaku; Yamane, Hisanori (August 2016). "Synthesis and crystal structure analysis of titanium bismuthide oxide, Ti8BiO7". Journal of Alloys and Compounds. 675: 377–380. doi:10.1016/j.jallcom.2016.03.096.
  7. Nuss, Jürgen; Jansen, Martin (March 2012). "On the Rare Earth Metal Bismuthide Oxides RE2BiO2 (RE = Nd, Tb, Dy, Ho)". Zeitschrift für anorganische und allgemeine Chemie. 638 (3–4): 611–613. doi:10.1002/zaac.201100529.
  8. Kim, Heejung; Kang, Chang-Jong; Kim, Kyoo; Shim, J. H.; Min, B. I. (2016-03-09). "Suppression of the charge density wave instability in R 2 O 2 Bi ( R = La, Er) due to large spin-orbit coupling". Physical Review B. 93 (12): 125116. Bibcode:2016PhRvB..93l5116K. doi:10.1103/PhysRevB.93.125116. ISSN 2469-9950.
  9. Mizoguchi, Hiroshi; Hosono, Hideo (2011-03-02). "A Metal−Insulator Transition in R 2 O 2 Bi with an Unusual Bi 2− Square Net (R = Rare Earth or Y)". Journal of the American Chemical Society. 133 (8): 2394–2397. doi:10.1021/ja111015p. ISSN 0002-7863.
  10. Benz, R. (1971-04-01). "Ce 2 O 2 Sb and Ce 2 O 2 Bi crystal structure". Acta Crystallographica Section B. 27 (4): 853–854. doi:10.1107/S0567740871003066. ISSN 0567-7408.
  11. Nuss, Jürgen; Wedig, Ulrich; Jansen, Martin (November 2011). "Geometric Variations and Electron Localizations in Intermetallics: The Case of La2Sb Type Compounds". Zeitschrift für anorganische und allgemeine Chemie. 637 (13): 1975–1981. doi:10.1002/zaac.201100331.
  12. Xia, Sheng-Qing; Bobev, Svilen (2010-12-15). "Dibarium tricadmium bismuthide(-I,-III) oxide, Ba 2 Cd 3−δ Bi 3 O". Acta Crystallographica Section E. 66 (12): i81. doi:10.1107/S1600536810046283. ISSN 1600-5368. PMC 3011431. PMID 21589204.
  13. Forbes, Scott; Yuan, Fang; Kosuda, Kosuke; Kolodiazhnyi, Taras; Mozharivskyj, Yurij (January 2016). "Synthesis, crystal structure, and physical properties of the Gd3BiO3 and Gd8Bi3O8 phases". Journal of Solid State Chemistry. 233: 252–258. Bibcode:2016JSSCh.233..252F. doi:10.1016/j.jssc.2015.10.004.
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