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Oxybismuthides

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Class of chemical compounds

Oxybismuthides orbismuthide oxides are chemical compounds formally containing the group BiO, with onebismuth and oneoxygen atom. The bismuth and oxygen are not bound together as inbismuthates, instead they make a separate presence bound to the cations (metals), and could be considered as a mixedbismuthide-oxide compound. So a compound with O_mBi_n requirescations to balance a negative charge of 2m+3n. The cations will have charges of +2 or +3. The trications are oftenrare earth elements oractinides. They are in the category ofoxypnictide 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

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formula	name	mw	structure	space group	cell	appearance	properties	supercondicting T_c	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				^[1]^[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			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				^[8]
(EuF)₂Ti₂Bi₂O			tetragonal	I4/mmm	a=4.1172c=21.2718				^[3]
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				^[9]
Pr₂BiO₂			tetragonal	I4/mmm					^[9]
Nd₂BiO₂			tetragonal	I4/mmm	a=3.99258 c=13.6663 V=217.851				^[9]
Ho₂BiO₂			tetragonal	I4/mmm	a=3.86212 c=13.2262 V=197.28				^[9]
Sm₂BiO₂			tetragonal	I4/mmm	a=3.95296 c=13.5083 V=211.074				^[9]
Sm₄Bi₂O									^[10]
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			^[11]
Gd₃BiO₃			monoclinic	C2/m					^[12]
Gd₈Bi₃O₈			monoclinic	C2/m		grey			^[12]
Ca₂RE₇Bi₅O₅						grey			^[1]
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]

References

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^^a ^b ^c ^d ^eForbes, 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.
^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.
^^a ^bZhai, 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.
^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.
^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.
^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.
^^a ^b ^c ^dNuss, 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.
^^a ^bKim, 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.
^^a ^b ^c ^d ^e ^fMizoguchi, 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.
^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.
^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.
^^a ^bForbes, 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.
^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.
^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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