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

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 470605090

| Name =

| ImageFile = Tetrasulfur-tetranitride.png

| ImageFile_Ref = {{chemboximage|correct|??}}

| ImageSize = 160

| ImageName = Stereo, skeletal formula of tetrasulfur tetranitride with some measurements

| ImageFileL1 = Tetrasulfur-tetranitride-from-xtal-2000-3D-balls.png

| ImageNameL1 = Ball and stick model of tetrasulfur tetranitride

| ImageNameR1 = Space-filling model of tetrasulfur tetranitride

| OtherNames = {{Ubl|Cyclic sulfur(III) nitride tetramer{{Citation needed|date=January 2011}}|Tetranitrogen tetrasulfide|1λ⁴,3,5λ⁴,7,2,4,6,8-Tetrathiatetrazocine{{Citation needed|date=January 2011}}

}}

| IUPACName = Tetrasulfur tetranitride

| SystematicName = 1,3,5,7-tetrathia-2,4,6,8-tetraazacyclooctan-2,4,6,8-tetrayl

| CASNo = 28950-34-7

| CASNo_Ref = {{cascite|correct|CAS}}

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = 9BXS997HR6

| PubChem = 141455

| ChemSpiderID = 124788

| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

| SMILES1 = N1=[S]N=[S]N=[S]N=[S]1

| StdInChI = 1S/N4S4/c1-5-2-7-4-8-3-6-1

| StdInChI_Ref = {{stdinchicite|correct|chemspider}}

| StdInChIKey = LTPQFVPQTZSJGS-UHFFFAOYSA-N

| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

| Formula = {{chem2|S4N4}}

| MolarMass = 184.287 g/mol

| Appearance = Vivid orange, opaque crystals

| MeltingPtC = 187

| Section3 =

| Section4 =

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| Section6 =

'''Tetrasulfur tetranitride''' is an [[inorganic compound]] with the [[chemical formula|formula]] {{chem2|S4N4|auto=1}}. This vivid orange, opaque [[crystalline]] compound is the most important binary [[sulfur nitride]], which are compounds that contain only the [[chemical element|elements]] [[sulfur]] and [[nitrogen]]. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding.<ref name="Greenwood">{{ cite book |last1= Greenwood |first1= N. N. |last2= Earnshaw |first2= A. |title= Chemical Elements |edition= 2nd |publisher= Butterworth-Heinemann |location= Boston, MA |year= 1997 |pages= 721–725 }}</ref><ref name=Chivers>{{cite book |last= Chivers |first= T. |title= A Guide To Chalcogen-Nitrogen Chemistry |publisher= World Scientific Publishing |location= Singapore |year= 2004 |isbn= 981-256-095-5 }}</ref>

Nitrogen and sulfur have similar [[electronegativity|electronegativities]]. [[Diagonal relationship|When the properties of atoms are so highly similar]], they often form extensive families of [[covalent]]ly bonded structures and compounds. Indeed, a large number of S-N and S-NH compounds are known with {{chem2|S4N4}} as their parent.

==Structure==

{{chem2|S4N4}} adopts an unusual “extreme cradle” structure, with D_2d [[symmetry group|point group symmetry]]. It can be viewed as a derivative of a (hypothetical) eight-membered ring (or more simply a 'deformed' eight-membered ring) of alternating sulfur and nitrogen atoms. The pairs of sulfur atoms across the ring are separated by 2.586&nbsp;[[Angstrom|Å]], resulting in a cage-like structure as determined by single crystal X-ray diffraction.<ref>{{cite journal |last1= Sharma |first1= B. D. |last2= Donohue |first2= J. |title= The Crystal and Molecular Structure of Sulfur Nitride, S₄N₄ |journal= [[Acta Crystallographica]] |year= 1963 |volume= 16 |issue= 9 |pages= 891–897 |doi= 10.1107/S0365110X63002401 |bibcode= 1963AcCry..16..891S }}</ref> The nature of the [[Annulation#Transannular interaction|transannular S–S interactions]] remains a matter of investigation because it is significantly shorter than the sum of the van der Waal's distances<ref>{{cite journal |title= A PM3 SCF-MO Study of the Structure and Bonding in the Cage Systems S₄N₄ and S₄N₄X (X = N⁺, N⁻, S, N₂S, P⁺, C, Si, B⁻ and Al⁻) |authorlink1= Henry Rzepa |last1= Rzepa |first1= H. S. |last2= Woollins |first2= J. D. |journal= [[Polyhedron (journal)|Polyhedron]] |year= 1990 |volume= 9 |issue= 1 |pages= 107–111 |doi= 10.1016/S0277-5387(00)84253-9 }}</ref> but has been explained in the context of [[molecular orbital theory]].<ref name="Greenwood" /> One pair of the transannular S atoms have valence 4, and the other pair of the transannular S atoms have valence 2.{{cn|date=October 2022}} The bonding in {{chem2|S4N4}} is considered to be [[delocalized]], which is indicated by the fact that the bond distances between neighboring sulfur and nitrogen atoms are nearly identical. {{chem2|S4N4}} has been shown to co-crystallize with [[benzene]] and the [[fullerene|{{chem2|C60}}]] molecule.<ref>{{cite journal |last1= Konarev |first1= D. V. |last2= Lyubovskaya |first2= R. N. |last3= Drichko |first3= N. V. |last4= Yudanova |first4= E. I. |last5= Shulga |first5= Yu. M. |last6= Litvinov |first6= A. L. |last7= Semkin |first7= V. N. |last8= Tarasov |first8= B. P. |display-authors= 3 |title= Donor-Acceptor Complexes of Fullerene C₆₀ with Organic and Organometallic Donors |journal= [[Journal of Materials Chemistry]] |year= 2000 |volume= 10 |issue= 4 |pages= 803–818 |doi= 10.1039/a907106g }}</ref>

==Properties==

{{chem2|S4N4}} is stable to [[air]]. It is, however, unstable in the [[thermodynamic]] sense with a positive [[enthalpy of formation]] of +460 kJ/mol. This [[endothermic]] enthalpy of formation originates in the difference in energy of {{chem2|S4N4}} compared to its highly stable decomposition products:

:{{chem2|2 S4N4 → 4 N2 + S8}}

Because one of its decomposition products is a gas, {{chem2|S4N4}} can be used as an explosive.<ref name="Greenwood" /> Purer samples tend to be more explosive. Small samples can be detonated by striking with a hammer. {{chem2|S4N4}} is [[thermochromic]], changing from pale yellow below −30&nbsp;°C to orange at room temperature to deep red above 100&nbsp;°C.<ref name="Greenwood" />

==Synthesis==

{{chem2|S4N4}} was first prepared in 1835 by M. Gregory by the reaction of [[disulfur dichloride]] with [[ammonia]],<ref>{{Cite journal| last1 = Jolly | first1 = W. L.| last2 = Lipp | first2 = S. A.| title = Reaction of Tetrasulfur Tetranitride with Sulfuric Acid| journal = Inorganic Chemistry | volume = 10 | issue = 1| pages = 33–38 | year = 1971| doi = 10.1021/ic50095a008| url = https://escholarship.org/uc/item/7xj1q0zf}}</ref> a process that has been optimized:<ref name="Blanco">{{cite book |last1= Villena-Blanco |first1= M. |last2= Jolly |first2= W. L. |chapter= Tetrasulfur Tetranitride, S₄N₄ |display-authors= etal |series= [[Inorganic Syntheses]] |year= 1967 |volume= 9 |pages= 98–102 |doi= 10.1002/9780470132401.ch26 |isbn= 978-0-470-13168-8 |title= Inorganic Syntheses |editor= S. Y. Tyree Jr}}</ref>

:{{chem2|6 S2Cl2 + 16 NH3 → S4N4 + S8 + 12 [NH4]Cl}}

Coproducts of this reaction include [[heptasulfur imide]] ({{chem2|S7NH}}) and elemental sulfur, and the latter equilibrates with more {{chem2|S4N4}} and [[ammonium sulfide]]:<ref>{{cite book|url=https://archive.org/details/cftri.2662nonaqueoussolven0000ludw/page/44/|p=44|title=Non-aqueous solvents|first1=Ludwig&nbsp;F.|last1=Audrieth|first2=Jacob|last2=Kleinberg|publisher=John Wiley & Sons|location=New York|year=1953|lccn=52-12057}}</ref>

:{{chem2|10 S + 16 NH3 ↔ N4S4 + 6 (NH4)S}}

A related synthesis employs {{chem2|[NH4]Cl}} instead:<ref name="Greenwood" />

:{{chem2|4 [NH4]Cl + 6 S2Cl2 → S4N4 + 16 HCl + S8}}

An alternative synthesis entails the use of {{chem2|(((CH3)3Si)2N)2S}} as a precursor with pre-formed S–N bonds. {{chem2|(((CH3)3Si)2N)2S}} is prepared by the reaction of [[lithium bis(trimethylsilyl)amide]] and [[sulfur dichloride|{{chem2|SCl2}}]].

:{{chem2|2 ((CH3)3Si)2NLi + SCl2 → (((CH3)3Si)2N)2S + 2 LiCl}}

The {{chem2|(((CH3)3Si)2N)2S}} reacts with the combination of {{chem2|SCl2}} and [[sulfuryl chloride|{{chem2|SO2Cl2}}]] to form {{chem2|S4N4}}, [[trimethylsilyl chloride]], and [[sulfur dioxide]]:<ref>{{cite book |last1= Maaninen |first1= A. |last2= Shvari |first2= J. |last3= Laitinen |first3= R. S. |last4= Chivers |first4=T |chapter= Compounds of General Interest |series= [[Inorganic Syntheses]] |year= 2002 |volume= 33 |pages= 196–199 |doi= 10.1002/0471224502.ch4 |editor-last= Coucouvanis |editor-first= Dimitri |title= Inorganic Syntheses|isbn= 9780471208259 }}</ref>

:{{chem2|2 (((CH3)3Si)2N)2S + 2 SCl2 + 2 SO2Cl2 → S4N4 + 8 (CH3)3SiCl + 2 SO2}}

==Acid-base reactions==

[[File:S4N4.BF3-from-xtal-1967-3D-balls.png|thumb|right|150px|{{chem2|S4N4*BF3}}]]

{{chem2|S4N4}} serves as a [[Lewis base]] by binding through nitrogen to strongly [[Lewis acid]]ic compounds such as [[Antimony pentachloride|{{chem2|SbCl5}}]] and [[Sulfur trioxide|{{chem2|SO3}}]]. The cage is distorted in these [[adducts]].<ref name="Greenwood" />

:{{chem2|S4N4 + SbCl5 → S4N4*SbCl5}}

:{{chem2|S4N4 + SO3 → S4N4*SO3}}

The reaction of {{chem2|[Pt2Cl4(P(CH3)2[[Phenyl|Ph]])2]}} with {{chem2|S4N4}} is reported to form a complex where a sulfur forms a dative bond to the metal. This compound upon standing is isomerised to a complex in which a nitrogen atom forms the additional bond to the metal centre.

It is protonated by [[Tetrafluoroboric acid|{{chem2|H[BF4]}}]] to form a [[tetrafluoroborate]] salt:

:{{chem2|S4N4 + H[BF4] → [S4N4H]+[BF4]−}}

The soft Lewis acid [[copper(I) chloride|CuCl]] forms a [[coordination polymer]]:<ref name="Greenwood" />

:{{chem2|''n'' S4N4 + ''n'' CuCl → (S4N4)_{''n''}\-μ\-(\sCu\sCl\s)_{''n''}|}}

Dilute [[sodium hydroxide|NaOH]] hydrolyzes {{chem2|S4N4}} as follows, yielding [[thiosulfate]] and [[trithionate]]:<ref name="Greenwood" />

:{{chem2|2 S4N4 + 6 OH− + 9 H2O → S2O3(2−) + 2 S3O6(2−) + 8 NH3}}

More concentrated [[base (chemistry)|base]] yields [[sulfite]]:

:{{chem2|S4N4 + 6 OH− + 3 H2O → S2O3(2−) + 2 SO3(2−) + 4 NH3}}

===Metal complexes===

{{chem2|S4N4}} reacts with metal complexes. The cage remains intact in some cases but in other cases, it is degraded.<ref name=Chivers/><ref>{{cite journal |last1= Kelly |first1= P. F. |last2= Slawin |first2= A. M. Z. |last3= Williams |first3= D. J. |last4= Woollins |first4= J. D. |title= Caged explosives: Metal-Stabilized Chalcogen Nitrides |journal= [[Chemical Society Reviews]] |year= 1992 |volume= 21 |issue= 4 |pages= 245–252 |doi= 10.1039/CS9922100245 }}</ref> {{chem2|S4N4}} reacts with [[Vaska's complex]] ({{chem2|[Ir(Cl)(CO)(P[[Phenyl|Ph]]3)2]}} in an [[oxidative addition]] reaction to form a six coordinate [[iridium]] complex where the {{chem2|S4N4}} binds through two sulfur atoms and one nitrogen atom.

=={{chem2|S4N4}} as a precursor to other S-N compounds==

Many S-N compounds are prepared from {{chem2|S4N4}}.<ref name="ch7">{{cite book |last1= Bojes |first1=J. |last2= Chivers |first2=T. |last3= Oakley |first3=R. D. |chapter=Binary Cyclic Nitrogen-Sulfur Anions |display-authors= etal |title= Inorganic Syntheses |series= [[Inorganic Syntheses]] |year= 1989 |volume= 25 |pages= 30–35 |doi= 10.1002/9780470132562.ch7 |editor-last= Allcock |editor-first= H. R. |isbn=9780470132562 }}</ref> Reaction with [[piperidine]] generates {{chem2|[S4N5]−}}:

:{{chem2|24 S4N4 + 32 C5H10NH → 8 [C5H10NH2]+[S4N5]− + 8 (C5H10N)2S + 3 S8 + 8 N2}}

A related [[cation]] is also known, i.e. {{chem2|[S4N5]+}}.

Treatment with [[Quaternary ammonium cation|tetramethylammonium]] [[azide]] produces the heterocycle {{chem2|[S3N3]−}}:

:{{chem2|8 S4N4 + 8 [(CH3)4N]+[N3]- → 8 [(CH3)4N]+[S3N3]- + S8 + 16 N2}}

''Cyclo''-{{chem2|[S3N3]−}} has 10 pi-electrons.

In a related reaction, the use of the [[bis(triphenylphosphine)iminium]] azide gives a salt containing the blue {{chem2|[NS4]−}} anion:<ref name="ch7" />

:{{chem2|4 S4N4 + 2 [PPN]+[N3]- → 2 [PPN]+[NS4]- + S8 + 10 N2}}

The anion {{chem2|[NS4]-}} has a chain structure described using the resonance {{chem2|[S\dS\dN\sS\sS−] ↔ [−S\sS\sN\dS\dS]}}.

{{chem2|S4N4}} reacts with electron-poor [[alkyne]]s.<ref>{{ cite journal |title= The Reaction Between Tetrasulphur Tetranitride (S₄N₄) and Electron-deficient Alkynes. A Molecular Orbital Study |last1= Dunn |first1= P. J. |authorlink2= Henry Rzepa |last2= Rzepa |first2= H. S. |journal= [[Journal of the Chemical Society, Perkin Transactions 2]] |year= 1987 |volume= 1987 |issue= 11 |pages= 1669–1670 |doi= 10.1039/p29870001669 }}</ref>

Chlorination of {{chem2|S4N4}} gives [[Thiazyl chloride trimer|thiazyl chloride]].

Passing gaseous {{chem2|S4N4}} over [[silver]] metal yields the low temperature [[superconductor]] [[polythiazyl]] or polysulfurnitride (transition temperature (0.26±0.03)&nbsp;K<ref>{{cite journal |last1= Greene |first1= R. L. |last2= Street |first2= G. B. |last3= Suter |first3= L. J. |title= Superconductivity in Polysulfur Nitride (SN)_x |journal= [[Physical Review Letters]] |year= 1975 |volume= 34 |issue= 10 |pages= 577–579 |doi= 10.1103/PhysRevLett.34.577 |bibcode= 1975PhRvL..34..577G}}</ref>), often simply called "(SN)_''x''". In the conversion, the [[silver]] first becomes sulfided, and the resulting [[silver sulfide|{{chem2|Ag2S}}]] catalyzes the conversion of the {{chem2|S4N4}} into the four-membered ring {{chem2|S2N2}}, which readily [[polymer]]izes.<ref name="Greenwood" />

:{{chem2|S4N4 + 8 Ag → 4 Ag2S + 2 N2}}

:{{chem2|''x'' S4N4 → (SN)_{4''x''}|}}

==Related compounds==

* The [[selenium]] analogue {{chem2|Se4N4}}, [[tetraselenium tetranitride]].

==Safety==

{{chem2|S4N4}} is shock-sensitive. Purer samples are more shock-sensitive than those contaminated with elemental sulfur.<ref name="Blanco"/>

==References==

{{Reflist|30em}}

{{sulfur compounds}}

{{Nitrides}}

[[Category:Explosive chemicals]]

[[Category:Inorganic compounds]]

[[Category:Sulfur–nitrogen compounds]]

[[Category:Nitrides]]

[[Category:Eight-membered rings]]