Oxybismuthides Explained
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 |
|---|
| Ti8BiO7 | octatitanium bismuthide heptoxide | | orthorhombic | Cmmm | I = 7.8473 Å, b = 16.829 Å, c = 3.0256 Å | silver | conductor | | [2] |
| (SrF)2Ti2Bi2O | | | tetragonal | I4/mmm | | | | | [3] |
| BaTi2Bi2O | | | tetragonal | | a = 4.046 Å, c = 7.272 Å | | | | [4] |
| LaNiBiO | Lanthanum nickel oxybismuthide | | | | | | | 4.2 | [5] |
| Ce2O2Bi | | | tetragonal | I4/mmm | a=4.034 c=13.736 | | | | [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 | | | |
| Dy2BiO2 | | 565.98 | tetragonal | I4/mmm | a=387.61 c=1323.3 V=198.82 | dark grey | | | |
| Ho2BiO2 | | 570.84 | tetragonal | I4/mmm | a=385.83 c=1321.8 V=196.77 | dark grey | | | |
| La2BiO2 | | | tetragonal | I4/mmm | a=4.08083 c=13.9866 V=198.74 | | | | [8] |
| Er2BiO2 | | | tetragonal | I4/mmm | a=3.84531 c=13.1513 V=194.48 | | | | |
| (EuF)2Ti2Bi2O | | | tetragonal | I4/mmm | a=4.1172 c=21.2718 | | | | |
| Gd2BiO2 | | | tetragonal | I4/mmm | a=3.9181 c=13.4246 V=206.09 | | | | [9] |
| Y2BiO2 | | | tetragonal | I4/mmm | a=3.8734 c=13.2469 V=198.74 | | | | |
| Pr2BiO2 | | | tetragonal | I4/mmm | | | | | |
| Nd2BiO2 | | | tetragonal | I4/mmm | a=3.99258 c=13.6663 V=217.851 | | | | |
| Ho2BiO2 | | | tetragonal | I4/mmm | a=3.86212 c=13.2262 V=197.28 | | | | |
| Sm2BiO2 | | | tetragonal | I4/mmm | a=3.95296 c=13.5083 V=211.074 | | | | |
| Sm4Bi2O | | | | | | | | | [10] |
| Eu4Bi2O | | | | | | | | | |
| Ba2Cd2.13Bi3O | Dibarium tricadmium bismuthide(-I,-III) oxide | | tetragonal | I4/mmm | a = 4.7396 c = 43.601 V=979.5 Z=4 | black | | | [11] |
| Gd3BiO3 | | | monoclinic | C2/m | | | | | [12] |
| Gd8Bi3O8 | | | monoclinic | C2/m | | grey | | | |
| Ca2RE7Bi5O5 | | | | | | grey | | | |
| Cm2BiO2 | | | tetragonal | I4/mmmm | a=3.957 c=13.359 | | | | [13] |
| Am2BiO2 | Americium dioxybismuthide | | orthorhombic | Pnam | a=5.053 b=8.092 c=5.738 | | | | [14] | |
Notes and References
- 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. en. 29. 22. 9605–9612. 10.1021/acs.chemmater.7b03996. 0897-4756.
- Amano. Shinsaku. Yamane. Hisanori. August 2016. Synthesis and crystal structure analysis of titanium bismuthide oxide, Ti8BiO7. Journal of Alloys and Compounds. en. 675. 377–380. 10.1016/j.jallcom.2016.03.096.
- 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 . en . 19232–19239 . 10.1021/acs.inorgchem.2c02895 . 36395178 . 253627945 . 0020-1669.
- 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. 10.1088/1468-6996/16/3/033503. 1468-6996. 5099821. 27877784. 2015STAdM..16c3503H. 1505.02240.
- Kozhevnikov . V. L. . Leonidova . O. N. . Ivanovskii . A. L. . Shein . I. R. . Goshchitskii . B. N. . Kar’kin . A. E. . New superconductor with a layered crystal structure: Nickel oxybismuthide LaO1−δNiBi . JETP Letters . 5 February 2009 . 87 . 11 . 649–651 . 10.1134/S002136400811012X. 120451483 .
- 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. 10.1107/S0567740871003066. 1971AcCrB..27..853B . 0567-7408.
- 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. en. 638. 3–4. 611–613. 10.1002/zaac.201100529.
- 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. en. 93. 12. 125116. 10.1103/PhysRevB.93.125116. 2469-9950. 2016PhRvB..93l5116K.
- 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. en. 133. 8. 2394–2397. 10.1021/ja111015p. 21302922. 0002-7863.
- 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. en. 637. 13. 1975–1981. 10.1002/zaac.201100331.
- 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. 10.1107/S1600536810046283. 1600-5368. 3011431. 21589204. 2010AcCrE..66I..81X .
- 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. en. 233. 252–258. 10.1016/j.jssc.2015.10.004. 2016JSSCh.233..252F.
- Book: Seaborg . G. T. . Katz . Joseph J. . Morss . L. R. . The Chemistry of the Actinide Elements . 2012 . Springer Science & Business Media . 978-94-009-3155-8 . 972 . en.
- Book: Seaborg . G. T. . Katz . Joseph J. . Morss . L. R. . The Chemistry of the Actinide Elements . 2012 . Springer Science & Business Media . 978-94-009-3155-8 . 902 . en.
