Trithiazyl trichloride

Trithiazyl trichloride
Names
	Other names thionitrosyl chloride
Identifiers
CAS Number	(trimer), 17178-58-4 (monomer) 5964-00-1 (trimer), 17178-58-4 (monomer);
3D model (JSmol)	Interactive image;
	InChI InChI=1S/Cl3N3S3/c1-7-4-8(2)6-9(3)5-7 Key: QBQMTUMJJWPFDJ-UHFFFAOYSA-N;
	SMILES ClS1=NS(Cl)=NS(Cl)=N1;
Properties
Chemical formula	Cl3N3S3
Molar mass	244.55 g·mol−1
Appearance	white solid
Melting point	168 ºC
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Trithiazyl trichloride is the inorganic compound with the formula S₃N₃Cl₃. It is a white solid. It is a reagent in main group chemistry,^[1] but has no commercial applications.

Structure

The molecule has C_3v symmetry. The S₃N₃ core is slightly ruffled structure with S-N distances of 160.5 pm. The three chloride groups are attached to sulfur with S-Cl distance of 208 pm, and are mutually cis, as the S centers are pyramidal. In contrast to the NSCl connectivity, nitrosyl chloride has the connectivity ONCl.^[2]^[3]

Synthesis and reactions

It is obtained by chlorination of tetrasulfur tetranitride:

³⁄₄ S₄N₄ + ³⁄₂ Cl₂ → S₃N₃Cl₃

At 100 ºC in vacuum, thiazyl chloride trimer undergoes cracking to thiazyl chloride monomer, which is a green gas.

S₃N₃Cl₃ → 3 NS-Cl

In NSCl, chloride is bonded to the chalcogen, in contrast to nitrosyl chloride with an N-Cl bond. In contrast, with six fewer electrons, cyanuric chloride is a planar ring.

It reacts with nitriles to dithiadiazolium chlorides:^[2]

RCN + ²⁄₃ S₃N₃Cl₃ → [RCN₂S₂]Cl + ¹⁄₂ Cl₂ + ¹⁄₂ N₂

The compound oxidizes to the S(VI) compound S₃N₃O₃Cl₃, which exists as isomers.

References

↑ William L. Jolly, Keith D. Maguire (1967). "Sulfur Nitrogen Chlorides". Inorg. Synth. IX. doi:10.1002/9780470132401.ch27.
1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
↑ Wiegers, G. A.; Vos, A. (1966). "The Crystal Structures of Two Sulfur-Nitrogen Compounds with (S-N)3 Rings. II. Trithiazylchloride, (NSCl)₃, at -130 C". Acta Crystallographica. 20: 192.

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[1] William L. Jolly, Keith D. Maguire (1967). "Sulfur Nitrogen Chlorides". Inorg. Synth. IX. doi:10.1002/9780470132401.ch27.

[G&E-2] 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.

[3] Wiegers, G. A.; Vos, A. (1966). "The Crystal Structures of Two Sulfur-Nitrogen Compounds with (S-N)3 Rings. II. Trithiazylchloride, (NSCl)₃, at -130 C". Acta Crystallographica. 20: 192.