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Bismuth oxynitrate
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<h2 id="hydrates">Hydrates</h2> <p>Bismuth oxynitrate is commercially available as Bi5O(OH)9(NO3)4 (CAS number: <a href="https://commonchemistry.cas.org/detail?cas_rn=1304-85-4&title=">1304-85-4</a> ) or as BiONO3·H2O (CAS Number: <a href="https://commonchemistry.cas.org/detail?cas_rn=13595-83-0&title=">13595-83-0</a> ). </p><p>Some compounds have been fully characterised with single crystal studies and found to contain the <a href="/facts/Octahedral_molecular_geometry/bNXLVvks">octahedral</a> [Bi6O<i>x</i>(OH)8−<i>x</i>](10−<i>x</i>)+ cation. There is indirect evidence that either the octahedral cation Bi6O4(OH)6+4<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> or the octahedral cation Bi6(OH)6+12<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> is present in aqueous solution following the <a href="/facts/Polymerisation/1hmBz7Ur">polymerisation</a> of Bi(H2O)3+8, the Bi3+ ion present in acidic solutions.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> The ion Bi6O4(OH)6+4 is found in the <a href="/facts/Perchlorate/WCC53zS2">perchlorate</a> compound Bi6O4(OH)4ClO4·7H2O<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> and is <a href="/facts/Isoelectronic/SbzuaI05">isoelectronic</a> with the octahedral Sn6O4(OH)4 cluster found in the hydrate of <a href="/facts/Tin(II)_oxide/X4BJM7kS">tin(II) oxide</a>, 3SnO·H2O.<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> The compounds that contain this are: </p> Bi6O4(HO)4(NO3)6·H2O<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a><a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> (equivalent to BiONO3·1/2H2O; Bi2O3·N2O5·H2O ) Bi6O4(OH)4(NO3)6·4H2O<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> (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+<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> <p>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.<a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a> </p><p>Additionally some oxynitrates have layer structures (a common motif also found in bismuth(III) <a href="/facts/Oxyhalides/vAppA4lU">oxyhalides</a>): </p> Bi2O2(OH)NO3 (equivalent to BiONO3·1/2H2O) contains "[Bi2O2]2+" layers<a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a> Bi5O7NO3, which is <a href="/facts/Isostructural/xWlgsQ95">isostructural</a> with β-Bi5O7I<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a> <h2 id="cluster-cation-structure">Cluster cation structure</h2> <p>The octahedral ion has 6 Bi3+ ions at the corners of an <a href="/facts/Octahedron/G38q92xW">octahedron</a>. 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 <a href="/facts/Ab_initio_quantum_chemistry_method/Rwuu2At1"><i>ab initio</i></a> theoretical study of the <a href="/facts/Hydration_reaction/T1Vb2u1d">hydration mechanism</a> of Bi3+ and the structure concludes that the <a href="/facts/Lone_pair/Q6kEAC4g">lone pairs</a> on the Bi3+ ions are <a href="/facts/Stereochemistry/XkcRVNwd">stereochemically</a> active.<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a> </p> <h2 id="preparation">Preparation</h2> <p>Bismuth oxynitrates can be prepared from <a href="/facts/Bismuth(III)_nitrate/vEF560s4">bismuth(III) nitrate</a>. 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 <a href="/facts/Thermal_decomposition/Qqx9RqkW">thermal decomposition</a> of the pentahydrate. </p><p>The thermal decomposition of bismuth nitrate pentahydrate proceeds through the following stages:<a class="footnote-ref" id="fnref:16" href="#fn:16"><sup>16</sup></a> </p> 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 <a href="/facts/Hydrolysis/JTvwIHPs">hydrolysis</a> occurs and Bi6O5(OH)3(NO3)5·3H2O is formed. <p>The final oxynitrate product of thermal dehydration is believed to be Bi5O7NO3,<a class="footnote-ref" id="fnref:17" href="#fn:17"><sup>17</sup></a> which is isostructural with β–Bi5O7I and has a layer structure.<a class="footnote-ref" id="fnref:18" href="#fn:18"><sup>18</sup></a> The ultimate stage of thermal decomposition of oxynitrates is <a href="/facts/Bismuth(III)_oxide/CyL3482j">bismuth(III) oxide</a>, Bi2O3. </p> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Sadler, Peter J (1991). Sykes, A.G. (ed.). Advances in Inorganic Chemistry. Vol. 36. Academic Press. ch. 1. ISBN 0-12-023636-2. <a href="0-12-023636-2" target="_blank">0-12-023636-2</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>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 <a href="0-12-352651-5" target="_blank">0-12-352651-5</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>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 <a href="0-12-352651-5" target="_blank">0-12-352651-5</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. <a href="978-0-08-037941-8" target="_blank">978-0-08-037941-8</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>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. <a href="https://doi.org/10.1351%2FPAC-CON-09-10-22" target="_blank">https://doi.org/10.1351%2FPAC-CON-09-10-22</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>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. <a href="0-7514-0389-X" target="_blank">0-7514-0389-X</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. <a href="978-0-08-037941-8" target="_blank">978-0-08-037941-8</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>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. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>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. <a href="https://doi.org/10.3891%2Facta.chem.scand.33a-0219" target="_blank">https://doi.org/10.3891%2Facta.chem.scand.33a-0219</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>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. <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> <li id="fn:11"><p>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. <a href="http://orbit.dtu.dk/files/6626676/Investigation%20of%20the%20crystal%20structure.pdf" target="_blank">http://orbit.dtu.dk/files/6626676/Investigation%20of%20the%20crystal%20structure.pdf</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li> <li id="fn:12"><p>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. <a href="/wiki/Acta_Crystallographica_Section_B" target="_blank">/wiki/Acta_Crystallographica_Section_B</a> <a href="#fnref:12" class="footnote-back-ref">↩</a></p></li> <li id="fn:13"><p>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. <a href="https://doi.org/10.1515%2Fznb-2005-0315" target="_blank">https://doi.org/10.1515%2Fznb-2005-0315</a> <a href="#fnref:13" class="footnote-back-ref">↩</a></p></li> <li id="fn:14"><p>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. <a href="/wiki/Journal_of_Solid_State_Chemistry" target="_blank">/wiki/Journal_of_Solid_State_Chemistry</a> <a href="#fnref:14" class="footnote-back-ref">↩</a></p></li> <li id="fn:15"><p>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. <a href="/wiki/Canadian_Journal_of_Chemistry" target="_blank">/wiki/Canadian_Journal_of_Chemistry</a> <a href="#fnref:15" class="footnote-back-ref">↩</a></p></li> <li id="fn:16"><p>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. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:16" class="footnote-back-ref">↩</a></p></li> <li id="fn:17"><p>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. <a href="/wiki/Journal_of_Solid_State_Chemistry" target="_blank">/wiki/Journal_of_Solid_State_Chemistry</a> <a href="#fnref:17" class="footnote-back-ref">↩</a></p></li> <li id="fn:18"><p>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. <a href="https://doi.org/10.1524%2Fncrs.2004.219.2.91" target="_blank">https://doi.org/10.1524%2Fncrs.2004.219.2.91</a> <a href="#fnref:18" class="footnote-back-ref">↩</a></p></li> </ol>