Bismuth oxynitrate

Bismuth oxynitrate

Names
IUPAC name pentabismuth;oxygen(2-);nonahydroxide;tetranitrate
Other names Bismuthyl nitrate Basic bismuth nitrate Bismuth subnitrate [USP:JAN] Bismutum subnitricum Magisterium bismuti
Identifiers
CAS Number	1304-85-4^Y
3D model (JSmol)	Interactive image
ChEBI	CHEBI:31293^Y
ChemSpider	65321938^Y
DrugBank	DB13209^Y
MeSH	bismuth+subnitrate
PubChem CID	73415757
UNII	H19J064BA5^Y
InChI InChI=1S/5Bi.4NO3.9H2O.O/c;;;;;4*2-1(3)4;;;;;;;;;;/h;;;;;;;;;9*1H2;/q5*+3;4*-1;;;;;;;;;;-2/p-9 Key: QGWDKKHSDXWPET-UHFFFAOYSA-E[1]
SMILES [N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[O-2].[Bi+3].[Bi+3].[Bi+3].[Bi+3].[Bi+3] [1]
Properties
Chemical formula	Bi5H9N4O22 (Basic formula) [1]
Molar mass	1461.99 g/mol [1]
Density	1.79 g/mL (H2O) [1]
Melting point	Decomposes at 260 [1]
Boiling point	Decomposes at 260 [1]
Solubility in water	Insoluble [1]
Hazards
GHS labelling:
Pictograms
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Bismuth subnitrate monohydrate

Names
IUPAC name oxobismuthanyl nitrate;hydrate
Identifiers
CAS Number	13595-83-0^Y
3D model (JSmol)	Interactive image
PubChem CID	129842132
InChI InChI=1S/Bi.NO3.H2O.O/c;2-1(3)4;;/h;;1H2;/q+1;-1;; Key: HFJNHTDBULDRRH-UHFFFAOYSA-N
SMILES [N+](=O)([O-])O[Bi]=O.O
Properties
Chemical formula	BiH2NO5 (Basic formula) [2]
Molar mass	305 g/mol [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Bismuth oxynitrate is the name applied to a number of compounds that contain Bi³⁺, nitrate ions and oxide ions and which can be considered as compounds formed from Bi₂O₃, N₂O₅ and H₂O. Other names for bismuth oxynitrate include bismuth subnitrate and bismuthyl nitrate. In older texts bismuth oxynitrate is often simply described as BiONO₃ or basic bismuth nitrate. Bismuth oxynitrate was once called magisterium bismuti or bismutum subnitricum, and was used as a white pigment, in beauty care, and as a gentle disinfectant for internal and external use.^[3][4] It is also used to form Dragendorff's reagent, which is used as a TLC stain.

Hydrates

Bismuth oxynitrate is commercially available as Bi₅O(OH)₉(NO₃)₄ (CAS number: 1304-85-4 ) or as BiONO₃·H₂O (CAS Number: 13595-83-0 ).

Some compounds have been fully characterised with single crystal studies and found to contain the octahedral [Bi₆O_x(OH)_8−x]^(10−x)+ cation. There is indirect evidence that either the octahedral cation Bi
₆O
₄(OH)⁶⁺
₄^[4] or the octahedral cation Bi
₆(OH)⁶⁺
₁₂^[5] is present in aqueous solution following the polymerisation of Bi(H
₂O)³⁺
₈, the Bi³⁺ ion present in acidic solutions.^[6] The ion Bi
₆O
₄(OH)⁶⁺
₄ is found in the perchlorate compound Bi₆O₄(OH)₄ClO₄·7H₂O^[7] and is isoelectronic with the octahedral Sn₆O₄(OH)₄ cluster found in the hydrate of tin(II) oxide, 3SnO·H₂O.^[5] The compounds that contain this are:

Bi₆O₄(HO)₄(NO₃)₆·H₂O^[8][9] (equivalent to BiONO₃·⁠1/2⁠H₂O; Bi₂O₃·N₂O₅·H₂O )

Bi₆O₄(OH)₄(NO₃)₆·4H₂O^[10] (equivalent to BiONO₃·H₂O; Bi₂O₃·N₂O₅·6H₂O )

[Bi₆O₄(OH)₄][Bi₆O₅(OH)₃](NO₃)₁₁, which contains two different cations, [Bi₆O₄(OH)₄]⁶⁺ and [Bi₆O₅(OH)₃]^5+[11]

The compound Bi₆O₅(OH)₃(NO₃)₅·3H₂O (equivalent to 6Bi₂O₃·5N₂O₅·9H₂O) also contains the octahedral units but this time they are joined to form {[Bi₆O₅(OH)₃]⁵⁺}₂.^[12]

Additionally some oxynitrates have layer structures (a common motif also found in bismuth(III) oxyhalides):

Bi₂O₂(OH)NO₃ (equivalent to BiONO₃·⁠1/2⁠H₂O) contains "[Bi₂O₂]²⁺" layers^[13]

Bi₅O₇NO₃, which is isostructural with β-Bi₅O₇I^[14]

Cluster cation structure

The octahedral ion has 6 Bi³⁺ ions at the corners of an octahedron. There is no covalent bond between the Bi atoms, they are held in position by bridging O²⁻ and OH⁻ anions, one at the centre of each of the eight triangular faces, bridging three Bi ions. The Bi ions are essentially four coordinate and are at the apex of a flat square pyramid. An ab initio theoretical study of the hydration mechanism of Bi³⁺ and the structure concludes that the lone pairs on the Bi³⁺ ions are stereochemically active.^[15]

Preparation

Bismuth oxynitrates can be prepared from bismuth(III) nitrate. For example, hydrolysis of a solution of bismuth nitrate through the addition of alkali or the reaction of the pentahydrate, BiNO₃·5H₂O with KOH, or the controlled thermal decomposition of the pentahydrate.

The thermal decomposition of bismuth nitrate pentahydrate proceeds through the following stages:^[16]

At pH below 1.0, Bi₆O₄(OH)₄(NO₃)₆·4H₂O (equivalent to BiNO₃·H₂O) is the first solid product, which when heated produces Bi₆H₂O(NO₃)O₄(OH)₄ (equivalent to BiNO₃.⁠1/2⁠H₂O).

Between pH 1.2 and 1.8, further hydrolysis occurs and Bi₆O₅(OH)₃(NO₃)₅·3H₂O is formed.

The final oxynitrate product of thermal dehydration is believed to be Bi₅O₇NO₃,^[14] which is isostructural with β–Bi₅O₇I and has a layer structure.^[17] The ultimate stage of thermal decomposition of oxynitrates is bismuth(III) oxide, Bi₂O₃.

References

1. PubChem. "Bismuth subnitrate". pubchem.ncbi.nlm.nih.gov. Retrieved 2020-11-11.
2. PubChem. "Bismuth subnitrate monohydrate". pubchem.ncbi.nlm.nih.gov. Retrieved 2020-11-23.
3. Sadler, Peter J (1991). Sykes, A.G. (ed.). Advances in Inorganic Chemistry. Vol. 36. Academic Press. ch. 1. ISBN 0-12-023636-2.
4. Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils (ed.), Inorganic Chemistry, translated by Eagleson, Mary; Brewer, William, San Diego/Berlin: Academic Press/De Gruyter, p. 771, ISBN 0-12-352651-5
5. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
6. Persson, Ingmar (2010). "Hydrated metal ions in aqueous solution: How regular are their structures?". Pure and Applied Chemistry. 82 (10): 1901–1917. doi:10.1351/PAC-CON-09-10-22. ISSN 0033-4545.
7. Godfrey, S.M.; et al. (1998). "Chapter 4". In Norman, N.C. (ed.). Chemistry of Arsenic, Antimony and Bismuth. Blackie Academic and Professional. ISBN 0-7514-0389-X.
8. Lazarini, F. (1979). "Bismuth basic nitrate [Bi6(H2O)(NO3)O4(OH)4](NO3)5". Acta Crystallographica Section B. 35 (2): 448–450. Bibcode:1979AcCrB..35..448L. doi:10.1107/S0567740879003745. ISSN 0567-7408.
9. Sundvall, Bengt; Elgsaeter, Arnljot; Oftedal, Gunnhild; Strand, Knut A.; Hoyer, Eberhard; Spiridonov, V. P.; Strand, T. G. (1979). "Crystal and Molecular Structure of Tetraoxotetrahydroxobismuth(III) Nitrate Monohydrate, Bi6O4(HO)4(NO3)6.H2O". Acta Chemica Scandinavica. 33a: 219–224. doi:10.3891/acta.chem.scand.33a-0219. ISSN 0904-213X.
10. Lazarini, F. (1979). "Tetra-μ³-hydroxo-tetra-μ³-oxo-hexabismuth (III) nitrate tetrahydrate, [Bi₆O₄(OH)₄](NO₃)₆·4H₂O". Crystal Structure Communications. 8: 69–74.
11. Nørlund Christensen, Axel; Lebech, Bente (2012). "Investigation of the crystal structure of a basic bismuth(III) nitrate with the composition [Bi₆O₄(OH)₄]_0.54(1)[Bi₆O₅(OH)₃]_0.46(1)(NO₃)_5.54(1)" (PDF). Dalton Transactions. 41 (7): 1971–1980. doi:10.1039/c1dt11646k. ISSN 1477-9226. PMID 22180862. S2CID 205791388.
12. Lazarini, F. (1978). "The crystal structure of a bismuth basic nitrate, [Bi₆O₅(OH)₃](NO₃)₅·3H₂O". Acta Crystallographica Section B. 34 (11): 3169–3173. Bibcode:1978AcCrB..34.3169L. doi:10.1107/S0567740878010419. ISSN 0567-7408.
13. Henry, Natacha; et al. (2005). "[Bi₂O₂]²⁺ layers in Bi₂O₂(OH)(NO₃): synthesis and structure determination". Zeitschrift für Naturforschung B. 60 (3): 322–327. doi:10.1515/znb-2005-0315. S2CID 197047627.
14. Kodama, Hiroshi (1994). "Synthesis of a New Compound, Bi₅O₇NO₃, by Thermal Decomposition". Journal of Solid State Chemistry. 112 (1): 27–30. Bibcode:1994JSSCh.112...27K. doi:10.1006/jssc.1994.1259. ISSN 0022-4596.
15. Pye, C C; Gunasekara, C M; Rudolph, W W (2007). "An ab initio investigation of bismuth hydration". Canadian Journal of Chemistry. 85 (11): 945–950. doi:10.1139/v07-108. ISSN 0008-4042.
16. Lazarini, F. (1981). "Thermal dehydration of some basic bismuth nitrates". Thermochimica Acta. 46 (1): 53–55. Bibcode:1981TcAc...46...53L. doi:10.1016/0040-6031(81)85076-9. ISSN 0040-6031.
17. Ziegler, P.; Ströbele, M.; Meyer, H.-J. (2004). "Crystal structure of pentabismuth heptaoxide nitrate, Bi₅O₇NO₃". Zeitschrift für Kristallographie – New Crystal Structures. 219 (2): 91–92. doi:10.1524/ncrs.2004.219.2.91. S2CID 201123614.