Trithiazyl trichloride

Trithiazyl trichloride is the inorganic compound with the formula (NSCl)3. A white solid, it is a precursor to other sulfur nitrides,[1] but has no commercial applications.

Trithiazyl trichloride
Names
Other names
thionitrosyl chloride
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/Cl3N3S3/c1-7-4-8(2)6-9(3)5-7
    Key: QBQMTUMJJWPFDJ-UHFFFAOYSA-N
  • monomer: InChI=1S/ClNS/c1-3-2
    Key: FWVIYFTZAHMHIO-UHFFFAOYSA-N
  • trimer: ClS1=NS(Cl)=NS(Cl)=N1
  • monomer: N#SCl
Properties
(NSCl)3
Molar mass 244.55 g·mol−1
Appearance white solid
Melting point 168 °C (334 °F; 441 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Structure

The molecule is a 6-membered ring of alternating nitrogen and sulfur atoms, where each sulfur atom is attached to one chlorine atom by a single bond. The molecule contains alternating single and double bonds in the S3N3 core. The molecule has C3v symmetry. The S3N3 core is slightly ruffled structure with S-N distances of 160.5 pm. The S-Cl distances are 208 pm, and the chlorine atoms are mutually cis. The S centers are tetravalent and pyramidal. In contrast to the NSCl connectivity, nitrosyl chloride has the connectivity ONCl.[2][3]

Synthesis and reactions

Trithiazyl trichloride is obtained by chlorination of tetrasulfur tetranitride:

3 S4N4 + 6 Cl2 → 4 (NSCl)3

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

(−N=S(−Cl)−)3 → 3 N≡S−Cl

In N≡S−Cl, chlorine is bonded to sulfur, in contrast to nitrosyl chloride O=N–Cl, where chlorine is bonded to nitrogen. In contrast, with six fewer electrons, cyanuric chloride is a planar ring.

It reacts with nitriles to dithiadiazolium chlorides:[2]

6 RCN + 4 (NSCl)3 → 6 [RCN2S2]+Cl− + 3 Cl2 + 3 N2

The compound oxidizes to the S(VI) compound (NSOCl)3, which exists as isomers.

References
  1. William L. Jolly, Keith D. Maguire (1967). "Sulfur Nitrogen Chlorides". Inorganic Syntheses. Inorg. Synth. Inorganic Syntheses. Vol. IX. p. 102. doi:10.1002/9780470132401.ch27. ISBN 9780470132401.{{cite book}}: CS1 maint: uses authors parameter (link)
  2. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  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 (2): 192. doi:10.1107/s0365110x66000410.
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