bismuth oxynitrate
{{chembox
| ImageFile_Ref = {{chemboximage|correct|??}}
| ImageFile = File:BismuthOxynitrate.png
| ImageFile1 =
| SystematicName =
| OtherNames = Bismuthyl nitrate
Basic bismuth nitrate
Bismuth subnitrate [USP:JAN]
Bismutum subnitricum
Magisterium bismuti
| IUPACName = pentabismuth;oxygen(2-);nonahydroxide;tetranitrate
| Name =
| Reference =
| Section1 = {{Chembox Identifiers
| InChI = 1S/5Bi.4NO3.9H2O.O/c;;;;;4*2-1(3)4;;;;;;;;;;/h;;;;;;;;;9*1H2;/q5*+3;4*-1;;;;;;;;;;-2/p-9
| InChIKey = QGWDKKHSDXWPET-UHFFFAOYSA-E
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 1304-85-4
| PubChem = 73415757
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 31293
| MeSHName = bismuth+subnitrate
| DrugBank_Ref = {{drugbankcite|correct|drugbank}}
| DrugBank = DB13209
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 65321938
| 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]
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = H19J064BA5
}}
| Section2 = {{Chembox Properties
| Formula = Bi5H9N4O22 (Basic formula) {{Cite web|last=PubChem|title=Bismuth subnitrate|url=https://pubchem.ncbi.nlm.nih.gov/compound/73415757|access-date=2020-11-11|website=pubchem.ncbi.nlm.nih.gov|language=en}}
| MolarMass = 1461.99{{nbsp}}g/mol
| Density = 1.79{{nbsp}}g/mL (H2O)
| MeltingPt = Decomposes at 260
| BoilingPt = Decomposes at 260
}}
| Section3 = {{Chembox Hazards
| MainHazards =
| FlashPt =
| AutoignitionPt =
|GHSPictograms = {{GHS03}} {{GHS exclamation mark}}}}
}}
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| ImageFile =
| ImageFile1 =
| SystematicName =
| OtherNames =
| IUPACName = oxobismuthanyl nitrate;hydrate
| Name = Bismuth subnitrate monohydrate
| Reference =
| Section1 = {{Chembox Identifiers
| InChI = InChI=1S/Bi.NO3.H2O.O/c;2-1(3)4;;/h;;1H2;/q+1;-1;;
| InChIKey = HFJNHTDBULDRRH-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 13595-83-0
| PubChem = 129842132
| SMILES = [N+](=O)([O-])O[Bi]=O.O
}}
| Section2 = {{Chembox Properties
| Formula = BiH2NO5 (Basic formula) {{Cite web|last=PubChem|title=Bismuth subnitrate monohydrate|url=https://pubchem.ncbi.nlm.nih.gov/compound/129842132|access-date=2020-11-23|website=pubchem.ncbi.nlm.nih.gov|language=en}}
| MolarMass = 305{{nbsp}}g/mol
}}
}}
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.{{cite book |last=Sadler |first=Peter J|editor-first=A.G. |editor-last=Sykes |title=Advances in Inorganic Chemistry|volume=36 |publisher=Academic Press |date=1991 |at=ch. 1|isbn=0-12-023636-2}}{{Holleman&Wiberg|page=771}} 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: {{CAS|1304-85-4}}) or as BiONO3·H2O (CAS Number: {{CAS|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 {{chem|Bi|6|O|4|(OH)|4|6+}} or the octahedral cation {{chem|Bi|6|(OH)|12|6+}} is present in aqueous solution following the polymerisation of {{chem|Bi(H|2|O)|8|3+}}, the Bi3+ ion present in acidic solutions.{{cite journal|last1=Persson|first1=Ingmar|title=Hydrated metal ions in aqueous solution: How regular are their structures?|journal=Pure and Applied Chemistry|volume=82|issue=10|year=2010|pages=1901–1917|issn=0033-4545|doi=10.1351/PAC-CON-09-10-22|doi-access=free}} The ion {{chem|Bi|6|O|4|(OH)|4|6+}} is found in the perchlorate compound Bi6O4(OH)4ClO4·7H2O{{cite book |last=Godfrey |first=S.M.|editor-first=N.C. |editor-last=Norman |title=Chemistry of Arsenic, Antimony and Bismuth |publisher=Blackie Academic and Professional |date=1998 |chapter=Chapter 4|isbn=0-7514-0389-X|display-authors=etal}} and is isoelectronic with the octahedral Sn6O4(OH)4 cluster found in the hydrate of tin(II) oxide, 3SnO·H2O.{{Greenwood&Earnshaw2nd}} The compounds that contain this are:
:Bi6O4(HO)4(NO3)6·H2O{{cite journal|last1=Lazarini|first1=F.|title=Bismuth basic nitrate [Bi6(H2O)(NO3)O4(OH)4](NO3)5|journal=Acta Crystallographica Section B|volume=35|issue=2|year=1979|pages=448–450|issn=0567-7408|doi=10.1107/S0567740879003745|bibcode=1979AcCrB..35..448L }}{{cite journal|last1=Sundvall|first1=Bengt|last2=Elgsaeter|first2=Arnljot|last3=Oftedal|first3=Gunnhild|last4=Strand|first4=Knut A.|last5=Hoyer|first5=Eberhard|last6=Spiridonov|first6=V. P.|last7=Strand|first7=T. G.|title=Crystal and Molecular Structure of Tetraoxotetrahydroxobismuth(III) Nitrate Monohydrate, Bi6O4(HO)4(NO3)6.H2O.|journal=Acta Chemica Scandinavica|volume=33a|year=1979|pages=219–224|issn=0904-213X|doi=10.3891/acta.chem.scand.33a-0219|doi-access=free}} (equivalent to BiONO3·{{sfrac|1|2}}H2O; Bi2O3·N2O5·H2O )
:Bi6O4(OH)4(NO3)6·4H2O{{cite journal|last=Lazarini|first=F.|title=Tetra-μ3-hydroxo-tetra-μ3-oxo-hexabismuth (III) nitrate tetrahydrate, [Bi6O4(OH)4](NO3)6·4H2O|journal=Crystal Structure Communications|volume=8|date=1979|pages=69–74}} (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+{{cite journal|last1=Nørlund Christensen|first1=Axel|last2=Lebech|first2=Bente|title=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)|journal=Dalton Transactions|volume=41|issue=7|year=2012|pages=1971–1980|issn=1477-9226|doi=10.1039/c1dt11646k|pmid=22180862 |s2cid=205791388 |url=http://orbit.dtu.dk/files/6626676/Investigation%20of%20the%20crystal%20structure.pdf}}
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.{{cite journal|last1=Lazarini|first1=F.|title=The crystal structure of a bismuth basic nitrate, [Bi6O5(OH)3](NO3)5·3H2O|journal=Acta Crystallographica Section B|volume=34|issue=11|year=1978|pages=3169–3173|issn=0567-7408|doi=10.1107/S0567740878010419|bibcode=1978AcCrB..34.3169L }}
Additionally some oxynitrates have layer structures (a common motif also found in bismuth(III) oxyhalides):
:Bi2O2(OH)NO3 (equivalent to BiONO3·{{sfrac|1|2}}H2O) contains "[Bi2O2]2+" layers{{cite journal|last=Henry |first=Natacha |display-authors=etal |title=[Bi2O2]2+ layers in Bi2O2(OH)(NO3): synthesis and structure determination.|journal=Zeitschrift für Naturforschung B |volume=60|issue=3|date=2005|pages=322–327|doi=10.1515/znb-2005-0315 |s2cid=197047627 |doi-access=free }}
:Bi5O7NO3, which is isostructural with β-Bi5O7I{{cite journal|last1=Kodama|first1=Hiroshi|title=Synthesis of a New Compound, Bi5O7NO3, by Thermal Decomposition|journal=Journal of Solid State Chemistry|volume=112|issue=1|year=1994|pages=27–30|issn=0022-4596|doi=10.1006/jssc.1994.1259|bibcode=1994JSSCh.112...27K }}
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.{{cite journal|last1=Pye|first1=C C|last2=Gunasekara|first2=C M|last3=Rudolph|first3=W W|title=An ab initio investigation of bismuth hydration|journal=Canadian Journal of Chemistry|volume=85|issue=11|year=2007|pages=945–950|issn=0008-4042|doi=10.1139/v07-108}}
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:{{cite journal|last1=Lazarini|first1=F.|title=Thermal dehydration of some basic bismuth nitrates|journal=Thermochimica Acta|volume=46|issue=1|year=1981|pages=53–55|issn=0040-6031|doi=10.1016/0040-6031(81)85076-9|bibcode=1981TcAc...46...53L }}
: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.{{sfrac|1|2}}H2O).
: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, which is isostructural with β–Bi5O7I and has a layer structure.{{cite journal|last1=Ziegler|first1=P.|first2=M.|last2=Ströbele|first3=H.-J.|last3=Meyer|title=Crystal structure of pentabismuth heptaoxide nitrate, Bi5O7NO3|journal=Zeitschrift für Kristallographie – New Crystal Structures|volume=219|issue=2|date=2004|pages=91–92|doi=10.1524/ncrs.2004.219.2.91 |s2cid=201123614 |doi-access=free}} The ultimate stage of thermal decomposition of oxynitrates is bismuth(III) oxide, Bi2O3.