Polythiazyl.docx

1. Polythiazyl
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Polythiazyl
Polythiazyl-2D-dimensions.png
(SN)x.png
Polythiazyl-chain-from-neutron-3D-vdW.png
Names
Othernames
polythiazyl
poly(sulfurnitride)
Identifiers
CASNumber
56422-03-8 ☒
ChemSpider
none
Properties
Chemical formula (SN)x
Appearance bronze colour,metalliclustre[1]
Exceptwhere otherwisenoted,dataare givenformaterialsintheirstandardstate (at25 °C [77 °F], 100
kPa).
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Infobox references
Polythiazyl(polymericsulfurnitride),(SN)x,isanelectricallyconductive,gold- orbronze-colored
polymerwithmetallicluster.Itwasthe firstconductive inorganicpolymerdiscovered[1][2] andwasalso
foundto be a superconductorat very low temperatures(below 0.26K).[3][4] Itis a fibroussolid,
describedas"lustrousgoldenonthe facesanddark blue-black",dependingonthe orientationof the
sample.Itisair stable andinsoluble inall solvents.[5]

2. Contents
1 History
2 Properties
2.1 Structure and bonding
3 Synthesis
4 Uses
5 Literature
6 References
History
The compoundwas firstreportedasearlyas 1910 byF.P.Burt, whoobtaineditby heatingtetrasulfur
tetranitride invacuumoversilverwool.[6]
The compoundwas the first non-metalliccompoundinwhichsuperconductivitycouldbe demonstrated.
However,the relativelylowtransitiontemperature atabout0.3 K makesa practical application
unlikely.[7][8]
Properties
Polythiazylisametallic-goldenandshiny,crystalline but fibrousmaterial.[8] The polymerismostlyinert
to oxygenandwater,butdecomposesinairto a greypowder.[9][10] Attemperaturesabove 240 °C
explosive decompositioncanoccur.[11] The compoundalsoexplodesonimpact.[10]
Polythiazylshowsananisotropicelectrical conductivity.Alongthe fibresorSN chains,the bondis
electricallyconductive,perpendiculartoitacts as an insulator.The one-dimensional conductivityis
basedon the bondingconditionsinthe S-N chain,where eachsulfuratomprovidestwoπelectronsand
each nitrogenatomprovidesone πelectrontoformtwo-center3πelectronbondingunits.[8]
Two polymorphiccrystal formswere observedinthe compound.The monoclinicformIobtainedfrom
the synthesiscanbe convertedintoanorthorhombicformIIby mechanical treatmentsuchas
grinding.[12]
Structure and bonding

3. The material isa polymer.The S andN atoms onadjacentchainsalign.[2][13][14] Several resonance
structurescan be written.[15]
Polythiazylresonance structures
The structure of the crystalline compoundwasresolvedbyX-raydiffraction.ThisshowedalternatingSN
bondlengthsof 159 pm and 163 pm and SNSbondanglesof 120 °C and NSN bondanglesof 106
°C.[16][17][9][8]
Synthesis
Polythiazylissynthesizedbythe polymerizationof the dimerdisulfurdinitride (S2N2),whichisinturn
synthesizedfromthe cyclicalternatingtetramertetrasulfurtetranitride(S4N4).[2] Conversionfrom
cyclictetramerto dimeriscatalysedwithhotsilverwool.[2][1][18]
S4N4 + 8 Ag → 4 Ag2S + 2 N2
S4N4 (w/Ag2S catalyst) → 2 S2N2 (w/77K cold finger) → S2N2
S2N2 (@ 0°C, sublimestosurface) → thermal polymerization→ (SN)x
Uses
Due to its electrical conductivity,polythiazyl isusedinLEDs,transistors,batterycathodes,andsolar
cells.[18]
Literature
King,R.S.P.:Novel chemistryandapplicationsof polythiazyl,Doctoral ThesisLoughboroughUniversity
2009, pdf-Download
References
Greenwood,NormanN.;Earnshaw,Alan(1997). Chemistryof the Elements(2nded.).Butterworth-
Heinemann.pp.725–727. ISBN 978-0-08-037941-8.
Goehring,Margot; Voigt,Dietrich(1953)."Über die Schwefelnitride (SN)2und(SN)x".Die
Naturwissenschaften(inGerman).40 (18): 482. Bibcode:1953NW.....40..482G. doi:10.1007/BF00628990.
ISSN 0028-1042. S2CID 8181710.
Labes,M. M.; Love,P.; Nichols,L.F.(1979). "PolysulfurNitride - aMetallic,SuperconductingPolymer".
Chemical Reviews.79(1):1–15. doi:10.1021/cr60317a002.

4. Harry R. Allcock(20 September2011). IntroductiontoMaterialsChemistry.John Wiley&Sons.p.131.
ISBN 978-1-118-21098-7. Retrieved29June 2012.
A. G. MacDiarmid;C. M. Mikulsk;A.J.Heeger;A.F. Garito (1983). "PolymericSulfurNitride
(Polythiazyl),(SN)X".PolymericSulfurNitride(Polythiazyl),(SN)x.InorganicSyntheses. Vol.22.pp.143–
149. doi:10.1002/9780470132531.ch31. ISBN 9780470132531.
Burt, Frank Playfair(1910)."XCIX.—A new sulphideof nitrogen".J.Chem.Soc.,Trans.97: 1171–1174.
doi:10.1039/CT9109701171. ISSN 0368-1645.
Labes,M.M.; Love,P.;Nichols,L.F.:Polysulfurnitride - ametallic,superconductingpolymerinChem.
Rev.79 (1979) 1–15, doi:10.1021/cr60317a002.
Alsfasser,R.;Janiak,C.;Klapötke,T.M.;Meyer,H.-J.:Moderne Anorganische Chemie,Herausgeber
Riedel,E.,3.Auflage 2007, Walterde GruyterGmbH & Co.KG, Berlin/Boston,ISBN 978-3-11-019060-1,
S. 129–132, (abgerufenüberDe GruyterOnline).
MacDiarmid,A.G.; Mikulski,C.M.;Saran,M.S.; Russo,P.J.;Cohen,M.J.;Bright,A.A.;Garito,A.F.;Heeger,
A.J.:SynthesisandSelectedProperties of PolymericSulfurNitride,(Polythiazyl),(SN)x inAdvancesin
Chemistry150 (2009) 63–72, doi:10.1021/ba-1976-0150.ch006.
Entry on Schwefel-Stickstoff-Verbindungen.at:RömppOnline.GeorgThiemeVerlag,retrieved2.März
2017.
Wiberg,E.; Wiberg,N.;Holleman,A.F.:AnorganischeChemie,103.Auflage,2017 Walterde Gruyter
GmbH & Co. KG, Berlin/Boston,ISBN 978-3-11-026932-1, S. 681, (abgerufenüberDe GruyterOnline).
Baughman,R.H.; Apgar,P.A.;Chance,R.R.;MacDiarmid,A.G.; Garito,A.F.:A New Phase of (SN)x inJ.
Chem.Soc.Chem.Comm.1977, 49–50, doi:10.1039/C39770000049.
Goehring,Margot (1956). "Sulphurnitride anditsderivatives".QuarterlyReviews,Chemical Society.10
(4): 437. doi:10.1039/qr9561000437. ISSN 0009-2681.
Cohen,M.J .; Garito,A. F.;Heeger,A.J.; MacDiarmid,A.G.; Mikulski,C.M.; Saran, M. S.; Kleppinger,J.
(1976). "Solidstate polymerizationof S2N2to (SN)x".Journal of the AmericanChemical Society.98:
3844–3848. doi:10.1021/ja00429a018.
Okada,M.; Tanaka, K.;Takata, A.;Yamabe,T. (1993). "Examinationof ElectronicPhase of the Hartree-
Fock Solutionof anIsolatedPolythiazyl Chain".SyntheticMetals.59 (2):223–230. doi:10.1016/0379-
6779(93)91029-2.
Boudeulle,M.:inCryst. Struct.Comm.4 (1975) 9–13.
MacDiarmid,A.G.; Mikulski,C.M.;Russo,P.J.;Saran,M.S.; Garito,A.F.;Heeger,A.J.:Synthesisand
structure of the polymericmetal,(SN)x,anditsprecursor,S2N2in J.Chem.Soc. Chem.Comm.1975,
476–477, doi:10.1039/C39750000476.
RonaldD. Archer(26 February2001). Inorganicand OrganometallicPolymers.JohnWiley&Sons.p.
213. ISBN 978-0-471-24187-4. Retrieved29June 2012.
Categories:InorganicpolymersNitridesSulfurcompoundsSuperconductors

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