Bismuth oxynitrate

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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
3D model (
JSmol
)
ChEBI
ChemSpider
DrugBank
MeSH bismuth+subnitrate
UNII
  • 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
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]
Insoluble [1]
Hazards
GHS labelling:
GHS03: Oxidizing GHS07: Exclamation mark
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Bismuth subnitrate monohydrate
Names
IUPAC name
oxobismuthanyl nitrate;hydrate
Identifiers
3D model (
JSmol
)
  • 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
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).

Bismuth oxynitrate is the name applied to a number of compounds that contain

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

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

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. ^ a b c d e f g h PubChem. "Bismuth subnitrate". pubchem.ncbi.nlm.nih.gov. Retrieved 2020-11-11.
  2. ^ a b PubChem. "Bismuth subnitrate monohydrate". pubchem.ncbi.nlm.nih.gov. Retrieved 2020-11-23.
  3. ISBN 0-12-023636-2
    .
  4. ^
    ISBN 0-12-352651-5
  5. ^
    ISBN 978-0-08-037941-8
    .
  6. ISSN 0033-4545
    .
  7. ISBN 0-7514-0389-X
    .
  8. ISSN 0567-7408
    .
  9. 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. S2CID 205791388
    .
  12. ISSN 0567-7408
    .
  13. S2CID 197047627
    .
  14. ^
    ISSN 0022-4596
    .
  15. ISSN 0008-4042
    .
  16. ISSN 0040-6031
    .
  17. S2CID 201123614
    .
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