Oxybismuthides

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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

formulanamemwstructurespace groupcellappearancepropertiessupercondicting Tcreference
Ti8BiO7octatitanium bismuthide heptoxideorthorhombicCmmmI = 7.8473 Å, b = 16.829 Å, c = 3.0256 Åsilverconductor [2]
(SrF)2Ti2Bi2OtetragonalI4/mmm [3]
BaTi2Bi2Otetragonala = 4.046 Å, c = 7.272 Å [4]
LaNiBiOLanthanum nickel oxybismuthide4.2 [5]
Ce2O2BitetragonalI4/mmma=4.034 c=13.736 [1] [6]
Nd2BiO2529.46tetragonalI4/mmma=399.11 c = 1366.3 V=217.53dark grey [7]
Tb2BiO2558.82tetragonalI4/mmma=389.62 c=1331.7 V=202.16dark grey [7]
Dy2BiO2565.98tetragonalI4/mmma=387.61 c=1323.3 V=198.82dark grey [7]
Ho2BiO2570.84tetragonalI4/mmma=385.83 c=1321.8 V=196.77dark grey [7]
La2BiO2tetragonalI4/mmma=4.08083 c=13.9866 V=198.74 [8]
Er2BiO2tetragonalI4/mmma=3.84531 c=13.1513 V=194.48 [8]
(EuF)2Ti2Bi2OtetragonalI4/mmma=4.1172 c=21.2718 [3]
Gd2BiO2tetragonalI4/mmma=3.9181 c=13.4246 V=206.09 [9]
Y2BiO2tetragonalI4/mmma=3.8734 c=13.2469 V=198.74 [9]
Pr2BiO2tetragonalI4/mmm [9]
Nd2BiO2tetragonalI4/mmma=3.99258 c=13.6663 V=217.851 [9]
Ho2BiO2tetragonalI4/mmma=3.86212 c=13.2262 V=197.28 [9]
Sm2BiO2tetragonalI4/mmma=3.95296 c=13.5083 V=211.074 [9]
Sm4Bi2O [10]
Eu4Bi2O [1]
Ba2Cd2.13Bi3ODibarium tricadmium bismuthide(-I,-III) oxidetetragonalI4/mmma = 4.7396 c = 43.601 V=979.5 Z=4black [11]
Gd3BiO3monoclinicC2/m [12]
Gd8Bi3O8monoclinicC2/mgrey [12]
Ca2RE7Bi5O5grey [1]
Cm2BiO2tetragonalI4/mmmma=3.957 c=13.359 [13]
Am2BiO2Americium dioxybismuthideorthorhombicPnama=5.053 b=8.092 c=5.738 [14]

References

  1. 1 2 3 4 5 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. ↑ 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.
  3. 1 2 Zhai, Hui-Fei; Jing, Yi-Shuai; Zhang, Pan; Lin, Bo; Song, Jia-Ming; Hu, Peng; Li, Bai-Zhuo; Du, Jian-Hua; Jiao, Zhi-Wei; Cao, Guang-Han (2022-11-17). "Structure and Physical Properties of the Layered Titanium-Based Pnictide Oxides (EuF) 2 Ti 2 Pn 2 O (Pn = Sb, Bi)". Inorganic Chemistry. 61 (48): 19232–19239. doi:10.1021/acs.inorgchem.2c02895. ISSN   0020-1669. PMID   36395178. S2CID   253627945.
  4. ↑ 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.
  5. ↑ 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. S2CID   120451483.
  6. ↑ 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. Bibcode:1971AcCrB..27..853B. doi:10.1107/S0567740871003066. ISSN   0567-7408.
  7. 1 2 3 4 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. 1 2 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" (PDF). Physical Review B. 93 (12): 125116. Bibcode:2016PhRvB..93l5116K. doi:10.1103/PhysRevB.93.125116. ISSN   2469-9950.
  9. 1 2 3 4 5 6 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. PMID   21302922.
  10. ↑ 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.
  11. ↑ 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. Bibcode:2010AcCrE..66I..81X. doi:10.1107/S1600536810046283. ISSN   1600-5368. PMC   3011431 . PMID   21589204.
  12. 1 2 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.
  13. ↑ 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.
  14. ↑ 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.
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