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Tetrasulfur tetranitride

January 01, 1970

Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This vivid orange, opaque crystalline compound is the most important binary sulfur nitride, which are compounds that contain only the elements sulfur and nitrogen. It is a precursor to many S-N compounds and has attracted wide interest for its unusual structure and bonding.[1][2]

Tetrasulfur tetranitride
Ball and stick model of tetrasulfur tetranitride
Space-filling model of tetrasulfur tetranitride
Names
IUPAC name
Tetrasulfur tetranitride
Systematic IUPAC name
1,3,5,7-tetrathia-2,4,6,8-tetraazacyclooctan-2,4,6,8-tetrayl
Other names
Identifiers
  • 28950-34-7 Y
3D model (JSmol)
  • Interactive image
ChemSpider
  • 124788 Y
  • 141455
UNII
  • 9BXS997HR6 Y
  • DTXSID20183147
  • InChI=1S/N4S4/c1-5-2-7-4-8-3-6-1 Y
    Key: LTPQFVPQTZSJGS-UHFFFAOYSA-N Y
  • N1=[S]N=[S]N=[S]N=[S]1
Properties
S4N4
Molar mass 184.287 g/mol
Appearance Vivid orange, opaque crystals
Melting point 187 °C (369 °F; 460 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)

Nitrogen and sulfur have similar electronegativities. When the properties of atoms are so highly similar, they often form extensive families of covalently bonded structures and compounds. Indeed, a large number of S-N and S-NH compounds are known with S4N4 as their parent.

Structure edit

S4N4 adopts an unusual “extreme cradle” structure, with D2d 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 Å, resulting in a cage-like structure as determined by single crystal X-ray diffraction.[3] The nature of the transannular S–S interactions remains a matter of investigation because it is significantly shorter than the sum of the van der Waal's distances[4] but has been explained in the context of molecular orbital theory.[1] One pair of the transannular S atoms have valence 4, and the other pair of the transannular S atoms have valence 2.[citation needed] The bonding in 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. S4N4 has been shown to co-crystallize with benzene and the C60 molecule.[5]

Properties edit

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 S4N4 compared to its highly stable decomposition products:

2 S4N4 → 4 N2 + S8

Because one of its decomposition products is a gas, S4N4 can be used as an explosive.[1] Purer samples tend to be more explosive. Small samples can be detonated by striking with a hammer. S4N4 is thermochromic, changing from pale yellow below −30 °C to orange at room temperature to deep red above 100 °C.[1]

Synthesis edit

S4N4 was first prepared in 1835 by M. Gregory by the reaction of disulfur dichloride with ammonia,[6] a process that has been optimized:[7]

6 S2Cl2 + 16 NH3 → S4N4 + S8 + 12 [NH4]Cl

Coproducts of this reaction include heptasulfur imide (S7NH) and elemental sulfur. A related synthesis employs [NH4]Cl instead:[1]

4 [NH4]Cl + 6 S2Cl2 → S4N4 + 16 HCl + S8

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

2 ((CH3)3Si)2NLi + SCl2 → (((CH3)3Si)2N)2S + 2 LiCl

The (((CH3)3Si)2N)2S reacts with the combination of SCl2 and SO2Cl2 to form S4N4, trimethylsilyl chloride, and sulfur dioxide:[8]

2 (((CH3)3Si)2N)2S + 2 SCl2 + 2 SO2Cl2 → S4N4 + 8 (CH3)3SiCl + 2 SO2

Acid-base reactions edit

 
S4N4·BF3

S4N4 serves as a Lewis base by binding through nitrogen to strongly Lewis acidic compounds such as SbCl5 and SO3. The cage is distorted in these adducts.[1]

S4N4 + SbCl5 → S4N4·SbCl5
S4N4 + SO3 → S4N4·SO3

The reaction of [Pt2Cl4(P(CH3)2Ph)2] with 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 H[BF4] to form a tetrafluoroborate salt:

S4N4 + H[BF4] → [S4N4H]+[BF4]−

The soft Lewis acid CuCl forms a coordination polymer:[1]

n S4N4 + n CuCl → (S4N4)n-μ-(−Cu−Cl−)n

Dilute NaOH hydrolyzes S4N4 as follows, yielding thiosulfate and trithionate:[1]

2 S4N4 + 6 OH− + 9 H2O → S2O2−3 + 2 S3O2−6 + 8 NH3

More concentrated base yields sulfite:

S4N4 + 6 OH− + 3 H2O → S2O2−3 + 2 SO2−3 + 4 NH3

Metal complexes edit

S4N4 reacts with metal complexes. The cage remains intact in some cases but in other cases, it is degraded.[2][9] S4N4 reacts with Vaska's complex ([Ir(Cl)(CO)(PPh3)2] in an oxidative addition reaction to form a six coordinate iridium complex where the S4N4 binds through two sulfur atoms and one nitrogen atom.

S4N4 as a precursor to other S-N compounds edit

Many S-N compounds are prepared from S4N4.[10] Reaction with piperidine generates [S4N5]−:

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

A related cation is also known, i.e. [S4N5]+.

Treatment with tetramethylammonium azide produces the heterocycle [S3N3]−:

8 S4N4 + 8 [(CH3)4N]+[N3]− → 8 [(CH3)4N]+[S3N3]− + S8 + 16 N2

Cyclo-[S3N3]− has 10 pi-electrons.

In a related reaction, the use of the bis(triphenylphosphine)iminium azide gives a salt containing the blue [NS4]− anion:[10]

4 S4N4 + 2 [PPN]+[N3]− → 2 [PPN]+[NS4]− + S8 + 10 N2

The anion [NS4]− has a chain structure described using the resonance [S=S=N−S−S−] ↔ [−S−S−N=S=S].

S4N4 reacts with electron-poor alkynes.[11]

Chlorination of S4N4 gives thiazyl chloride.

Passing gaseous S4N4 over silver metal yields the low temperature superconductor polythiazyl or polysulfurnitride (transition temperature (0.26±0.03) K[12]), often simply called "(SN)x". In the conversion, the silver first becomes sulfided, and the resulting Ag2S catalyzes the conversion of the S4N4 into the four-membered ring S2N2, which readily polymerizes.[1]

S4N4 + 8 Ag → 4 Ag2S + 2 N2
x S4N4 → (SN)4x

Related compounds edit

Safety edit

S4N4 is shock-sensitive. Purer samples are more shock-sensitive than those contaminated with elemental sulfur.[7]

References edit

  1. ^ a b c d e f g h i Greenwood, N. N.; Earnshaw, A. (1997). Chemical Elements (2nd ed.). Boston, MA: Butterworth-Heinemann. pp. 721–725.
  2. ^ a b Chivers, T. (2004). A Guide To Chalcogen-Nitrogen Chemistry. Singapore: World Scientific Publishing. ISBN 981-256-095-5.
  3. ^ Sharma, B. D.; Donohue, J. (1963). "The Crystal and Molecular Structure of Sulfur Nitride, S4N4". Acta Crystallographica. 16 (9): 891–897. Bibcode:1963AcCry..16..891S. doi:10.1107/S0365110X63002401.
  4. ^ Rzepa, H. S.; Woollins, J. D. (1990). "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−)". Polyhedron. 9 (1): 107–111. doi:10.1016/S0277-5387(00)84253-9.
  5. ^ Konarev, D. V.; Lyubovskaya, R. N.; Drichko, N. V.; et al. (2000). "Donor-Acceptor Complexes of Fullerene C60 with Organic and Organometallic Donors". Journal of Materials Chemistry. 10 (4): 803–818. doi:10.1039/a907106g.
  6. ^ Jolly, W. L.; Lipp, S. A. (1971). "Reaction of Tetrasulfur Tetranitride with Sulfuric Acid". Inorganic Chemistry. 10 (1): 33–38. doi:10.1021/ic50095a008.
  7. ^ a b Villena-Blanco, M.; Jolly, W. L.; et al. (1967). "Tetrasulfur Tetranitride, S4N4". In S. Y. Tyree Jr (ed.). Inorganic Syntheses. Inorganic Syntheses. Vol. 9. pp. 98–102. doi:10.1002/9780470132401.ch26. ISBN 978-0-470-13168-8.
  8. ^ Maaninen, A.; Shvari, J.; Laitinen, R. S.; Chivers, T (2002). "Compounds of General Interest". In Coucouvanis, Dimitri (ed.). Inorganic Syntheses. Inorganic Syntheses. Vol. 33. pp. 196–199. doi:10.1002/0471224502.ch4. ISBN 9780471208259.
  9. ^ Kelly, P. F.; Slawin, A. M. Z.; Williams, D. J.; Woollins, J. D. (1992). "Caged explosives: Metal-Stabilized Chalcogen Nitrides". Chemical Society Reviews. 21 (4): 245–252. doi:10.1039/CS9922100245.
  10. ^ a b Bojes, J.; Chivers, T.; Oakley, R. D.; et al. (1989). "Binary Cyclic Nitrogen-Sulfur Anions". In Allcock, H. R. (ed.). Inorganic Syntheses. Inorganic Syntheses. Vol. 25. pp. 30–35. doi:10.1002/9780470132562.ch7. ISBN 9780470132562.
  11. ^ Dunn, P. J.; Rzepa, H. S. (1987). "The Reaction Between Tetrasulphur Tetranitride (S4N4) and Electron-deficient Alkynes. A Molecular Orbital Study". Journal of the Chemical Society, Perkin Transactions 2. 1987 (11): 1669–1670. doi:10.1039/p29870001669.
  12. ^ Greene, R. L.; Street, G. B.; Suter, L. J. (1975). "Superconductivity in Polysulfur Nitride (SN)x". Physical Review Letters. 34 (10): 577–579. Bibcode:1975PhRvL..34..577G. doi:10.1103/PhysRevLett.34.577.

January 01, 1970
tetrasulfur, tetranitride, inorganic, compound, with, formula, s4n4, this, vivid, orange, opaque, crystalline, compound, most, important, binary, sulfur, nitride, which, compounds, that, contain, only, elements, sulfur, nitrogen, precursor, many, compounds, at. Tetrasulfur tetranitride is an inorganic compound with the formula S4N4 This vivid orange opaque crystalline compound is the most important binary sulfur nitride which are compounds that contain only the elements sulfur and nitrogen It is a precursor to many S N compounds and has attracted wide interest for its unusual structure and bonding 1 2 Tetrasulfur tetranitride Ball and stick model of tetrasulfur tetranitride Space filling model of tetrasulfur tetranitride Names IUPAC name Tetrasulfur tetranitride Systematic IUPAC name 1 3 5 7 tetrathia 2 4 6 8 tetraazacyclooctan 2 4 6 8 tetrayl Other names Cyclic sulfur III nitride tetramer citation needed Tetranitrogen tetrasulfide1l4 3 5l4 7 2 4 6 8 Tetrathiatetrazocine citation needed Identifiers CAS Number 28950 34 7 Y 3D model JSmol Interactive image ChemSpider 124788 Y PubChem CID 141455 UNII 9BXS997HR6 Y CompTox Dashboard EPA DTXSID20183147 InChI InChI 1S N4S4 c1 5 2 7 4 8 3 6 1 YKey LTPQFVPQTZSJGS UHFFFAOYSA N Y SMILES N1 S N S N S N S 1 Properties Chemical formula S4N4 Molar mass 184 287 g mol Appearance Vivid orange opaque crystals Melting point 187 C 369 F 460 K Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references Nitrogen and sulfur have similar electronegativities When the properties of atoms are so highly similar they often form extensive families of covalently bonded structures and compounds Indeed a large number of S N and S NH compounds are known with S4N4 as their parent Contents 1 Structure 2 Properties 3 Synthesis 4 Acid base reactions 4 1 Metal complexes 5 S4N4 as a precursor to other S N compounds 6 Related compounds 7 Safety 8 ReferencesStructure editS4N4 adopts an unusual extreme cradle structure with D2d 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 A resulting in a cage like structure as determined by single crystal X ray diffraction 3 The nature of the transannular S S interactions remains a matter of investigation because it is significantly shorter than the sum of the van der Waal s distances 4 but has been explained in the context of molecular orbital theory 1 One pair of the transannular S atoms have valence 4 and the other pair of the transannular S atoms have valence 2 citation needed The bonding in 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 S4N4 has been shown to co crystallize with benzene and the C60 molecule 5 Properties editS4N4 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 S4N4 compared to its highly stable decomposition products 2 S4N4 4 N2 S8 Because one of its decomposition products is a gas S4N4 can be used as an explosive 1 Purer samples tend to be more explosive Small samples can be detonated by striking with a hammer S4N4 is thermochromic changing from pale yellow below 30 C to orange at room temperature to deep red above 100 C 1 Synthesis editS4N4 was first prepared in 1835 by M Gregory by the reaction of disulfur dichloride with ammonia 6 a process that has been optimized 7 6 S2Cl2 16 NH3 S4N4 S8 12 NH4 Cl Coproducts of this reaction include heptasulfur imide S7NH and elemental sulfur A related synthesis employs NH4 Cl instead 1 4 NH4 Cl 6 S2Cl2 S4N4 16 HCl S8 An alternative synthesis entails the use of CH3 3Si 2N 2S as a precursor with pre formed S N bonds CH3 3Si 2N 2S is prepared by the reaction of lithium bis trimethylsilyl amide and SCl2 2 CH3 3Si 2NLi SCl2 CH3 3Si 2N 2S 2 LiCl The CH3 3Si 2N 2S reacts with the combination of SCl2 and SO2Cl2 to form S4N4 trimethylsilyl chloride and sulfur dioxide 8 2 CH3 3Si 2N 2S 2 SCl2 2 SO2Cl2 S4N4 8 CH3 3SiCl 2 SO2Acid base reactions edit nbsp S4N4 BF3 S4N4 serves as a Lewis base by binding through nitrogen to strongly Lewis acidic compounds such as SbCl5 and SO3 The cage is distorted in these adducts 1 S4N4 SbCl5 S4N4 SbCl5 S4N4 SO3 S4N4 SO3 The reaction of Pt2Cl4 P CH3 2Ph 2 with 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 H BF4 to form a tetrafluoroborate salt S4N4 H BF4 S4N4H BF4 The soft Lewis acid CuCl forms a coordination polymer 1 n S4N4 n CuCl S4N4 n m Cu Cl n Dilute NaOH hydrolyzes S4N4 as follows yielding thiosulfate and trithionate 1 2 S4N4 6 OH 9 H2O S2O2 3 2 S3O2 6 8 NH3 More concentrated base yields sulfite S4N4 6 OH 3 H2O S2O2 3 2 SO2 3 4 NH3 Metal complexes edit S4N4 reacts with metal complexes The cage remains intact in some cases but in other cases it is degraded 2 9 S4N4 reacts with Vaska s complex Ir Cl CO PPh3 2 in an oxidative addition reaction to form a six coordinate iridium complex where the S4N4 binds through two sulfur atoms and one nitrogen atom S4N4 as a precursor to other S N compounds editMany S N compounds are prepared from S4N4 10 Reaction with piperidine generates S4N5 24 S4N4 32 C5H10NH 8 C5H10NH2 S4N5 8 C5H10N 2S 3 S8 8 N2 A related cation is also known i e S4N5 Treatment with tetramethylammonium azide produces the heterocycle S3N3 8 S4N4 8 CH3 4N N3 8 CH3 4N S3N3 S8 16 N2 Cyclo S3N3 has 10 pi electrons In a related reaction the use of the bis triphenylphosphine iminium azide gives a salt containing the blue NS4 anion 10 4 S4N4 2 PPN N3 2 PPN NS4 S8 10 N2 The anion NS4 has a chain structure described using the resonance S S N S S S S N S S S4N4 reacts with electron poor alkynes 11 Chlorination of S4N4 gives thiazyl chloride Passing gaseous S4N4 over silver metal yields the low temperature superconductor polythiazyl or polysulfurnitride transition temperature 0 26 0 03 K 12 often simply called SN x In the conversion the silver first becomes sulfided and the resulting Ag2S catalyzes the conversion of the S4N4 into the four membered ring S2N2 which readily polymerizes 1 S4N4 8 Ag 4 Ag2S 2 N2 x S4N4 SN 4xRelated compounds editThe selenium analogue Se4N4 tetraselenium tetranitride Safety editS4N4 is shock sensitive Purer samples are more shock sensitive than those contaminated with elemental sulfur 7 References edit a b c d e f g h i Greenwood N N Earnshaw A 1997 Chemical Elements 2nd ed Boston MA Butterworth Heinemann pp 721 725 a b Chivers T 2004 A Guide To Chalcogen Nitrogen Chemistry Singapore World Scientific Publishing ISBN 981 256 095 5 Sharma B D Donohue J 1963 The Crystal and Molecular Structure of Sulfur Nitride S4N4 Acta Crystallographica 16 9 891 897 Bibcode 1963AcCry 16 891S doi 10 1107 S0365110X63002401 Rzepa H S Woollins J D 1990 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 Polyhedron 9 1 107 111 doi 10 1016 S0277 5387 00 84253 9 Konarev D V Lyubovskaya R N Drichko N V et al 2000 Donor Acceptor Complexes of Fullerene C60 with Organic and Organometallic Donors Journal of Materials Chemistry 10 4 803 818 doi 10 1039 a907106g Jolly W L Lipp S A 1971 Reaction of Tetrasulfur Tetranitride with Sulfuric Acid Inorganic Chemistry 10 1 33 38 doi 10 1021 ic50095a008 a b Villena Blanco M Jolly W L et al 1967 Tetrasulfur Tetranitride S4N4 In S Y Tyree Jr ed Inorganic Syntheses Inorganic Syntheses Vol 9 pp 98 102 doi 10 1002 9780470132401 ch26 ISBN 978 0 470 13168 8 Maaninen A Shvari J Laitinen R S Chivers T 2002 Compounds of General Interest In Coucouvanis Dimitri ed Inorganic Syntheses Inorganic Syntheses Vol 33 pp 196 199 doi 10 1002 0471224502 ch4 ISBN 9780471208259 Kelly P F Slawin A M Z Williams D J Woollins J D 1992 Caged explosives Metal Stabilized Chalcogen Nitrides Chemical Society Reviews 21 4 245 252 doi 10 1039 CS9922100245 a b Bojes J Chivers T Oakley R D et al 1989 Binary Cyclic Nitrogen Sulfur Anions In Allcock H R ed Inorganic Syntheses Inorganic Syntheses Vol 25 pp 30 35 doi 10 1002 9780470132562 ch7 ISBN 9780470132562 Dunn P J Rzepa H S 1987 The Reaction Between Tetrasulphur Tetranitride S4N4 and Electron deficient Alkynes A Molecular Orbital Study Journal of the Chemical Society Perkin Transactions 2 1987 11 1669 1670 doi 10 1039 p29870001669 Greene R L Street G B Suter L J 1975 Superconductivity in Polysulfur Nitride SN x Physical Review Letters 34 10 577 579 Bibcode 1975PhRvL 34 577G doi 10 1103 PhysRevLett 34 577 Retrieved from https en wikipedia org w index php title Tetrasulfur tetranitride amp oldid 1222261629, wikipedia, wiki, book, books, library,

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