Tetrasulfur dinitride

Structural formula
General
Surname	Tetrasulfur dinitride
Molecular formula	S 4 N 2
Brief description	dark red solid
External identifiers / databases
Wikidata	Q10812717
properties
Molar mass	156.28 g mol −1
Physical state	firmly
density	1.71 g cm −3 (supercooled melt)
Melting point	23 ° C
safety instructions
GHS hazard labeling ; no classification available
GHS hazard labeling ; no classification available
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Tetrasulfur dinitride is an inorganic chemical compound from the group of covalent nitrides . In addition to pentasulfur hexanitride , tetrasulfur tetranitride , disulfur dinitride , monosulfur mononitride , oligosulfur dinitrides and polymeric polythiazyl (SN) _x , the compound belongs to the group of sulfur-nitrogen compounds or sulfur nitrides .

history

The compound was first established in 1897 by Wilhelm Muthmann and E. Clever, the compound being mistaken for a nitrogen pentasulfide S ₅ N ₂ . In the early literature, various chain and ring structures were postulated for the compound. The sum formula S ₄ N ₂ could be determined by A. Meuwsen in 1951 by means of cryoscopy . The real structure as a six-membered ring with the nitrogen atoms in the 1- and 3-positions was discovered in 1971 by Henry G. Heal using ¹⁵ N- NMR spectroscopy , IR spectroscopy , Raman spectroscopy , UV-VIS spectroscopy , mass spectrometry and dipole measurements proven.

Extraction and presentation

Tetrasulfur dinitride can be obtained by reacting tetrasulphur tetranitride with sulfur at 110 ° C.

{\ displaystyle \ mathrm {S_ {4} N_ {4} +4 \ S \ longrightarrow 2 \ S_ {4} N_ {2}}}

A second synthetic route that avoids the explosive tetrasulphur tetranitride starts with heptasulphurimide, which is converted into the mercury salt by means of mercury (II) acetate . This then breaks down into mercury (II) sulfide , tetrasulfur dinitride and sulfur.

{\ displaystyle \ mathrm {2 \ S_ {7} NH + Hg (CH_ {3} COO) _ {2} \ longrightarrow Hg (S_ {7} N) _ {2} +2 \ CH_ {3} COOH}}

{\ displaystyle \ mathrm {Hg (S_ {7} N) _ {2} \ longrightarrow HgS + S_ {4} N_ {2} +9/8 \ S_ {8}}}

properties

Tetrasulfur dinitride is a less stable diamagnetic dark red solid which decomposes within a few hours at 0 ° C. At 100 ° C explosive decomposition to sulfur and nitrogen takes place . The compound is soluble in many organic solvents such as. B. benzene , nitrobenzene , carbon disulfide , carbon tetrachloride and diethyl ether , only moderately soluble in alcohols, but insoluble in water. A slow hydrolysis takes place with water, which is considerably accelerated in the basic medium. The compound is relatively stable to dilute acids.

The tetrasulfur dinitride molecule forms a non-planar six-membered ring in a half-chair shape , with the atoms S-N = S = N-S lying in one plane and bridged by a sulfur atom lying above this plane.

A stable adduct with the composition S ₄ N ₂ · 2BF _{3 is} formed with boron trifluoride . This only begins to decompose above 240 ° C.

Individual evidence

^ ^A ^b A. F. Holleman , E. Wiberg , N. Wiberg : Textbook of Inorganic Chemistry . 101st edition. Walter de Gruyter, Berlin 1995, ISBN 3-11-012641-9 , p. 604.
↑ ^a ^b ^c ^d ^e ^f ^g ^h Goehring, M .; Herb, H .; Wissemaier, H .: About the tetrasulfur dinitride S ₄ N ₂ in Z. anorg. allg. Chem. 267 (1952) 238-246, doi : 10.1002 / zaac.19522670406 .
↑ ^a ^b ^c ^d Georg Brauer (Ed.), With the collaboration of Marianne Baudler a . a .: Handbook of Preparative Inorganic Chemistry. 3rd, revised edition. Volume I, Ferdinand Enke, Stuttgart 1975, ISBN 3-432-02328-6 , p. 404.
↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
↑ Muthmann, W .; Clever, E .: About the nitrogen pentasulfide in Z. anorg. gen. Chem. 13 (1897) 200-208, doi : 10.1002 / zaac.18970130123 .
↑ Meuwsen, A .: About the tetrasulfur dinitride S ₄ N ₂ in Z. anorg. allg. Chem. 266 (1951) 250-255, doi : 10.1002 / zaac.19512660409 .
↑ Nelson, J .; Heal, HG: Structure of tetrasulphur dinitride in J. Chem. Soc. A, 1971, 136-139, doi : 10.1039 / J19710000136 .
↑ Heal, HG; Ramsay, RJ: A new, safe preparation of tetrasulphur dinitride in J. Inorg. Nucl. Chem. 37 (1975) 286, doi : 10.1016 / 0022-1902 (75) 80172-2 .
↑ Zhu, J.-K .; Gimarc, BM: Structure of tetrasulfur dinitride in Inorg. Chem. 22 (1983) 1996-1999, doi : 10.1021 / ic00156a014 .

[Arnold_F._Holleman,_Egon_Wiberg,_Nils_Wiberg-1] A ^b A. F. Holleman , E. Wiberg , N. Wiberg : Textbook of Inorganic Chemistry . 101st edition. Walter de Gruyter, Berlin 1995, ISBN 3-11-012641-9 , p. 604.

[Goehring-2] ↑ ^a ^b ^c ^d ^e ^f ^g ^h Goehring, M .; Herb, H .; Wissemaier, H .: About the tetrasulfur dinitride S ₄ N ₂ in Z. anorg. allg. Chem. 267 (1952) 238-246, doi : 10.1002 / zaac.19522670406 .

[brauer-3] Georg Brauer (Ed.), With the collaboration of Marianne Baudler a . a .: Handbook of Preparative Inorganic Chemistry. 3rd, revised edition. Volume I, Ferdinand Enke, Stuttgart 1975, ISBN 3-432-02328-6 , p. 404.

[NV-4] This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.

[Muthmann-5] Muthmann, W .; Clever, E .: About the nitrogen pentasulfide in Z. anorg. gen. Chem. 13 (1897) 200-208, doi : 10.1002 / zaac.18970130123 .

[6] Meuwsen, A .: About the tetrasulfur dinitride S ₄ N ₂ in Z. anorg. allg. Chem. 266 (1951) 250-255, doi : 10.1002 / zaac.19512660409 .

[Heal-7] Nelson, J .; Heal, HG: Structure of tetrasulphur dinitride in J. Chem. Soc. A, 1971, 136-139, doi : 10.1039 / J19710000136 .

[8] Heal, HG; Ramsay, RJ: A new, safe preparation of tetrasulphur dinitride in J. Inorg. Nucl. Chem. 37 (1975) 286, doi : 10.1016 / 0022-1902 (75) 80172-2 .

[9] Zhu, J.-K .; Gimarc, BM: Structure of tetrasulfur dinitride in Inorg. Chem. 22 (1983) 1996-1999, doi : 10.1021 / ic00156a014 .