Bismuth oxynitrate

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. 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]

Bismuth oxynitrate
Names
IUPAC name
pentabismuth;oxygen(2-);nonahydroxide;tetranitrate
Other names
Basic bismuth nitrate
Bismuth subnitrate [USP:JAN]
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
DrugBank
ECHA InfoCard 100.030.708
MeSH bismuth+subnitrate
UNII
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]
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
3D model (JSmol)
ECHA InfoCard 100.030.708
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).
Infobox references

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 [Bi6Ox(OH)8−x](10-x)+ cation. There is indirect evidence that either the octahedral cation Bi6O4(OH)46+[4] or the octahedral cation Bi6(OH)126+[5] is present in aqueous solution following the polymerisation of Bi(H2O)83+, the Bi3+ ion present in acidic solutions.[6] The ion Bi6O4(OH)46+ 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 BiONO3·0.5 H2O; Bi2O3.N2O5.H2O )
Bi6O4(OH)4(NO3)6.4H2O[10](equivalent to BiONO3·H2O; Bi2O3.N2O5.6H2O )
[Bi6O4.5(OH)3.5]2(NO3)11 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 BiONO3·0.5 H2O) 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 of bismuth oxynitrates

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 1, Bi6O4(OH)4(NO3)6.4H2O (BiNO3.H2O)is the first solid product, which when heated produced Bi6H2O(NO3)O4(OH)4 (BiNO3. 0.5H2O.
Between pH 1.2 and pH 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). "Chapter 1". In Sykes, A.G. (ed.). ADVANCES IN INORGANIC CHEMISTRY, Volume 36. Academic Press. 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. 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. "Tetra-μ 3-hydroxo-tetra-μ 3-oxo-hexabismuth (III) nitrate tetrahydrate,[Bi 6 O 4 (OH) 4](NO 3) 6• 4H 2 O." Cryst. Struct. Comm 8 (1979): 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. doi:10.1039/c1dt11646k. ISSN 1477-9226.
  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. doi:10.1107/S0567740878010419. ISSN 0567-7408.
  13. Henry, Natacha, et al. "[Bi2O2] 2+ layers in Bi2O2 (OH)(NO3): synthesis and structure determination." Zeitschrift für Naturforschung. B, A journal of chemical sciences 60.3 (2005): 322-327
  14. Kodama, Hiroshi (1994). "Synthesis of a New Compound, Bi5O7NO3, by Thermal Decomposition". Journal of Solid State Chemistry. 112 (1): 27–30. 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. doi:10.1016/0040-6031(81)85076-9. ISSN 0040-6031.
  17. Ziegler, P., M. Ströbele, and H-J. Meyer. "Crystal structure of pentabismuth heptaoxide nitrate, Bi5O7NO3." Zeitschrift für Kristallographie. New crystal structures 219.2 (2004): 91-92
Salts and covalent derivatives of the nitrate ion
HNO3 He
LiNO3 Be(NO3)2 B(NO
3)−
4		 RONO2 NO−
3
NH4NO3		 HOONO2 FNO3 Ne
NaNO3 Mg(NO3)2 Al(NO3)3 Si P S ClONO2 Ar
KNO3 Ca(NO3)2 Sc(NO3)3 Ti(NO3)4 VO(NO3)3 Cr(NO3)3 Mn(NO3)2 Fe(NO3)2
Fe(NO3)3		 Co(NO3)2
Co(NO3)3		 Ni(NO3)2 CuNO3
Cu(NO3)2		 Zn(NO3)2 Ga(NO3)3 Ge As Se Br Kr
RbNO3 Sr(NO3)2 Y(NO3)3 Zr(NO3)4 Nb Mo Tc Ru(NO3)3 Rh(NO3)3 Pd(NO3)2
Pd(NO3)4		 AgNO3
Ag(NO3)2		 Cd(NO3)2 In(NO3)3 Sn Sb(NO3)3 Te INO3 Xe(NO3)2
CsNO3 Ba(NO3)2   Hf(NO3)4 Ta W Re Os Ir Pt(NO3)2
Pt(NO3)4		 Au(NO3)3 Hg2(NO3)2
Hg(NO3)2		 TlNO3
Tl(NO3)3		 Pb(NO3)2 Bi(NO3)3
BiO(NO3)		 Po(NO3)4 At Rn
FrNO3 Ra(NO3)2   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La(NO3)3 Ce(NO3)3
Ce(NO3)4		 Pr(NO3)3 Nd(NO3)3 Pm(NO3)3 Sm(NO3)3 Eu(NO3)3 Gd(NO3)3 Tb(NO3)3 Dy(NO3)3 Ho(NO3)3 Er(NO3)3 Tm(NO3)3 Yb(NO3)3 Lu(NO3)3
Ac(NO3)3 Th(NO3)4 PaO2(NO3)3 UO2(NO3)2 Np(NO3)4 Pu(NO3)4 Am(NO3)3 Cm(NO3)3 Bk Cf Es Fm Md No Lr
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