Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Polythiazyl: Difference between pages

| verifiedrevid = 464210357

| ImageFile1 = (SN)x.png

| OtherNames = polythiazyl<br />poly(sulfur nitride)

|Section1={{Chembox Identifiers

| CASNo = 56422-03-8

| CASNo_Ref = {{cascite|changed|??}}

| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}

| ChemSpiderID = none

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|Section2={{Chembox Properties

| Formula = {{chem2|(SN)_{''x''}|}}

| Appearance = Golden or bronze-coloured crystalline solid with metallic lustre<ref name="G&E">{{ Greenwood&Earnshaw | pages = 725–727}}</ref>

| Solubility =}}

|Section3={{Chembox Hazards

| AutoignitionPt =}}

'''Polythiazyl''' ([[polymer]]ic [[sulfur]] [[nitrogen|nitride]]), {{chem2|(SN)_{''x''}|}}, is an [[electrical conductor|electrically conductive]], gold- or bronze-colored polymer with [[lustre (mineralogy)|metallic luster]]. It was the first conductive [[inorganic polymer]] discovered<ref name="G&E" /><ref name=":02">{{Cite journal|last1=Goehring|first1=Margot|last2=Voigt|first2=Dietrich|date=1953|title=Über die Schwefelnitride (SN)2 und (SN)x|journal=Die Naturwissenschaften|language=de|volume=40|issue=18|pages=482|doi=10.1007/BF00628990|bibcode=1953NW.....40..482G|s2cid=8181710|issn=0028-1042}}</ref> and was also found to be a [[superconductor]] at very low temperatures (below 0.26 K).<ref>{{ cite journal | title = Polysulfur Nitride - a Metallic, Superconducting Polymer |author1=Labes, M. M. |author2=Love, P. |author3=Nichols, L. F. | journal = [[Chemical Reviews]] | year = 1979 | volume = 79 | issue = 1 | pages = 1–15 | doi = 10.1021/cr60317a002}}</ref><ref name="Allcock2011">{{cite book|author=Harry R. Allcock|title=Introduction to Materials Chemistry|url=https://books.google.com/books?id=CnnbJG7f7dwC&pg=PT131|accessdate=29 June 2012|date=20 September 2011|publisher=John Wiley & Sons|isbn=978-1-118-21098-7|page=131}}</ref> It is a fibrous solid, described as "lustrous golden on the faces and dark blue-black", depending on the orientation of the sample. It is air stable and insoluble in all solvents.<ref>{{cite book|author1=A. G. MacDiarmid|author2=C. M. Mikulsk|author3-link=A. J. Heeger|author3=A. J. Heeger|author4=A. F. Garito|series=Inorganic Syntheses|title=Polymeric Sulfur Nitride (Polythiazyl), (SN)_x|chapter=Polymeric Sulfur Nitride (Polythiazyl), (SN) X|year=1983|volume=22|pages=143–149|doi=10.1002/9780470132531.ch31|isbn=9780470132531|author1-link=A. G. MacDiarmid}}</ref>

==History==

The compound was first reported as early as 1910 by F.P. Burt, who obtained it by heating [[tetrasulfur tetranitride]] in vacuum over silver wool.<ref>{{Cite journal|last=Burt|first=Frank Playfair|date=1910|title=XCIX.—A new sulphide of nitrogen|journal=J. Chem. Soc., Trans.|language=en|volume=97|pages=1171–1174|doi=10.1039/CT9109701171|issn=0368-1645|url=https://zenodo.org/record/2250224}}</ref>

The compound was the first compound with only non-metallic elements in which [[superconductivity]] could be demonstrated. However, the relatively low [[Superconductivity|transition temperature]] at about 0.3 K makes a practical application unlikely.<ref>Labes, M.M.; Love, P.; Nichols, L.F.: ''Polysulfur nitride - a metallic, superconducting polymer'' in [[Chem. Rev.]] 79 (1979) 1–15, {{doi|10.1021/cr60317a002}}.</ref><ref name="Riedel">Alsfasser, R.; Janiak, C.; Klapötke, T.M.; Meyer, H.-J.: ''Moderne Anorganische Chemie'', Herausgeber Riedel, E., 3. Auflage 2007, Walter de Gruyter GmbH & Co. KG, Berlin/Boston, {{ISBN|978-3-11-019060-1}}, S. 129–132, (retrieved via [[Verlag Walter de Gruyter|De Gruyter]] Online).</ref>

== Properties ==

Polythiazyl is a metallic-golden and shiny, crystalline but fibrous material.<ref name="Riedel"/> The polymer is mostly inert to oxygen and water, but decomposes in air to a grey powder.<ref name="MacDiarmid"/><ref name=Roempp>{{RömppOnline|Name=Schwefel-Stickstoff-Verbindungen |Datum=2 March 2017 |ID=RD-19-01408}}</ref> At temperatures above 240&nbsp;°C explosive decomposition can occur.<ref name="Holleman-Wiberg2017">[[Egon Wiberg|Wiberg, E.]]; [[Nils Wiberg|Wiberg, N.]]; [[Arnold F. Holleman|Holleman, A.F.]]: ''[[Holleman-Wiberg Lehrbuch der Anorganischen Chemie|Anorganische Chemie]]'', 103. Auflage, 2017 Walter de Gruyter GmbH & Co. KG, Berlin/Boston, {{ISBN|978-3-11-026932-1}}, S. 681, (retrieved via [[Verlag Walter de Gruyter|De Gruyter]] Online).</ref> The compound also explodes on impact.<ref name="Roempp" /> Explosion generally proceeds via decomposition to the elements.

Polythiazyl shows an anisotropic electrical conductivity. Along the fibres or SN chains, the bond is electrically conductive, perpendicular to it acts as an insulator. The one-dimensional conductivity is based on the bonding conditions in the S-N chain, where each sulfur atom provides two π electrons and each nitrogen atom provides one π electron to form two-center 3π electron bonding units.<ref name="Riedel" />

Two polymorphic crystal forms were observed in the compound. The monoclinic form I obtained from the synthesis can be converted into an orthorhombic form II by mechanical treatment such as grinding.<ref name="Baughman">Baughman, R.H.; Apgar, P.A.; Chance, R.R.; MacDiarmid, A.G.; Garito, A.F.: ''A New Phase of (SN)_x'' in [[J. Chem. Soc.]] Chem. Comm. 1977, 49–50, {{doi|10.1039/C39770000049}}.</ref>

===Structure and bonding===

The material is a polymer, containing trivalent nitrogen, and divalent and tetravalent sulfur. The S and N atoms on adjacent chains align.<ref name=":02" /><ref>{{Cite journal|last=Goehring|first=Margot|date=1956|title=Sulphur nitride and its derivatives|journal=Quarterly Reviews, Chemical Society|language=en|volume=10|issue=4|pages=437|doi=10.1039/qr9561000437|issn=0009-2681}}</ref><ref>{{cite journal|title=Solid state polymerization of S₂N₂ to (SN)_x|author1=Cohen, M.J .|author2=Garito, A. F.|author3=Heeger, A. J.|author4=MacDiarmid, A. G.|author5=Mikulski, C. M.|author6=Saran, M. S.|author7=Kleppinger, J. |journal=Journal of the American Chemical Society|year=1976|volume=98|pages=3844–3848|doi=10.1021/ja00429a018}}</ref> Several [[resonance structures]] can be written.<ref>{{ cite journal | title = Examination of Electronic Phase of the Hartree-Fock Solution of an Isolated Polythiazyl Chain |author1=Okada, M. |author2=Tanaka, K. |author3=Takata, A. |author4=Yamabe, T. | journal = Synthetic Metals | volume = 59 | issue = 2 | year = 1993 | pages = 223–230 | doi = 10.1016/0379-6779(93)91029-2}}</ref>

:[[Image:Polythiazyl resonance structures.svg | 440px|Polythiazyl resonance structures]]

The structure of the crystalline compound was resolved by [[X-ray diffraction]]. This showed alternating S–N bond lengths of 159 pm and 163 pm and S–N–S bond angles of 120 ° and N–S–N bond angles of 106 °.<ref>Boudeulle, M.: in [[Cryst. Struct. Comm.]] 4 (1975) 9–13.</ref><ref>MacDiarmid, A.G.; Mikulski, C.M.; Russo, P.J.; Saran, M.S.; Garito, A.F.;

Heeger, A.J.: ''Synthesis and structure of the polymeric metal, (SN)_x, and its precursor, S₂N₂'' in [[J. Chem. Soc.]] Chem. Comm. 1975, 476–477, {{doi|10.1039/C39750000476}}.</ref><ref name="MacDiarmid">MacDiarmid, A.G.; Mikulski, C.M.; Saran, M.S.; Russo, P.J.; Cohen, M.J.; Bright, A.A.; Garito, A.F.; Heeger, A.J.: ''Synthesis and Selected Properties of Polymeric Sulfur Nitride, (Polythiazyl), (SN)_x'' in [[Advances in Chemistry]] 150 (2009) 63–72, {{doi|10.1021/ba-1976-0150.ch006}}.</ref><ref name="Riedel" />

==Synthesis==

Polythiazyl is synthesized by the [[polymerization]] of the cyclic formal dimer [[disulfur dinitride]] ({{chem2|S2N2}}), which is in turn synthesized from the formal [[tetramer]] [[tetrasulfur tetranitride]] ({{chem2|S4N4}}),<ref name=":02" /> in the presence of hot [[silver]] wool.<ref name=":02" /><ref name="G&E" /><ref name="Archer2001" />

The reaction begins when silver abstracts sulfur from {{chem2|S4N4}} to produce a {{chem2|Ag2S}} catalyst; the resulting gaseous {{chem2|S2N2}} is then isolated through [[sublimation (phase transition)|sublimation]] onto a [[cold finger|cold surface]]:

:S₄N₄&nbsp;+ 8&nbsp;Ag → 4&nbsp;Ag₂S&nbsp;+ 2&nbsp;N₂

:S₄N₄ (low-pressure gas at 250-300&nbsp;°C; Ag₂S catalyst)&nbsp;→ 2&nbsp;S₂N₂ (gas)&nbsp;→ 2&nbsp;S₂N₂ (stable solid at 77&nbsp;[[Kelvin|K]])

When warmed to [[room temperature]], the additional heat induces spontaneous polymerization:

:S₂N₂ (0&nbsp;°C)&nbsp;→ (SN)_x

==Uses==

Due to its electrical conductivity, polythiazyl is used in [[LED]]s, [[transistor]]s, battery cathodes, and [[solar cell]]s.<ref name="Archer2001">{{cite book|author=Ronald D. Archer|title=Inorganic and Organometallic Polymers|url=https://books.google.com/books?id=9KFwwpv6bGcC&pg=PA213|accessdate=29 June 2012|date=26 February 2001|publisher=John Wiley & Sons|isbn=978-0-471-24187-4|page=213}}</ref>

== Literature ==

King, R.S.P.: ''Novel chemistry and applications of polythiazyl'', Doctoral Thesis Loughborough University 2009, [https://dspace.lboro.ac.uk/dspace-jspui/handle/2134/12571 pdf-Download]

==References==

{{reflist}}

[[Category:Inorganic polymers]]

[[Category:Nitrides]]

[[Category:Superconductors]]

[[Category:Sulfur–nitrogen compounds]]

[[Category:Conductive polymers]]