Trithiazyl trichloride

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Trithiazyl trichloride
ThiazylchlorideTrimer.svg
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Names
Other names
thionitrosyl chloride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • 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
Appearancewhite 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).

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.

Contents

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 or thiazyl fluoride monomer: [4]

3 S4N4 + 6 Cl2 → 4 (NSCl)3
3 FSN + 3 Cl2 → (NSCl)3 + 3 ClF

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.

Alkoxide or silver salts displace the chlorides: [5]

(-NS(Cl)-)3 + 3 NaOR → (-NS(OR)-)3 + 3 NaCl
(-NS(Cl)-)3 + 3 AgX → (-NS(X)-)3 + 3 AgCl

Treating thiazyl chloride with sulfur in the presence of antimony pentachloride gives dithionitronium hexachloroantimonate: [6]

SNCl + S + SbCl5 → [NS2]SbCl6

It reacts with nitriles to dithiadiazolium chlorides: [2]

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

Sulfur trioxide successively oxidizes the compound at the sulfur atoms to (NSOCl)3, [4] which exists as stereoisomers.

Related Research Articles

In chemistry, halogenation is a chemical reaction which introduces one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

<span class="mw-page-title-main">Titanium tetrachloride</span> Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4", as a phonetic representation of the symbols of its molecular formula.

<span class="mw-page-title-main">Nitrogen trichloride</span> Chemical compound

Nitrogen trichloride, also known as trichloramine, is the chemical compound with the formula NCl3. This yellow, oily, and explosive liquid is most commonly encountered as a product of chemical reactions between ammonia-derivatives and chlorine. Alongside monochloramine and dichloramine, trichloramine is responsible for the distinctive 'chlorine smell' associated with swimming pools, where the compound is readily formed as a product from hypochlorous acid reacting with ammonia and other nitrogenous substances in the water, such as urea from urine.

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

<span class="mw-page-title-main">Phosphorus trichloride</span> Chemical compound

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

<span class="mw-page-title-main">Tetrasulfur tetranitride</span> Chemical compound

Tetrasulfur tetranitride is an inorganic compound with the formula S4N4. This vivid orange, opaque, crystalline explosive 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.

<span class="mw-page-title-main">Scandium chloride</span> Chemical compound

Scandium(III) chloride is the inorganic compound with the formula ScCl3. It is a white, high-melting ionic compound, which is deliquescent and highly water-soluble. This salt is mainly of interest in the research laboratory. Both the anhydrous form and hexahydrate (ScCl3•6H2O) are commercially available.

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<span class="mw-page-title-main">Sulfur tetrafluoride</span> Chemical compound

Sulfur tetrafluoride is a chemical compound with the formula SF4. It is a colorless corrosive gas that releases dangerous hydrogen fluoride gas upon exposure to water or moisture. Sulfur tetrafluoride is a useful reagent for the preparation of organofluorine compounds, some of which are important in the pharmaceutical and specialty chemical industries.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

<span class="mw-page-title-main">Metal nitrosyl complex</span> Complex of a transition metal bonded to nitric oxide: Me–NO

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<span class="mw-page-title-main">Nitrosyl chloride</span> Chemical compound

Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.

<span class="mw-page-title-main">Gallium(III) chloride</span> Chemical compound

Gallium(III) chloride is an inorganic chemical compound with the formula GaCl3 which forms a monohydrate, GaCl3·H2O. Solid gallium(III) chloride is a deliquescent white solid and exists as a dimer with the formula Ga2Cl6. It is colourless and soluble in virtually all solvents, even alkanes, which is truly unusual for a metal halide. It is the main precursor to most derivatives of gallium and a reagent in organic synthesis.

<span class="mw-page-title-main">Beryllium chloride</span> Chemical compound

Beryllium chloride is an inorganic compound with the formula BeCl2. It is a colourless, hygroscopic solid that dissolves well in many polar solvents. Its properties are similar to those of aluminium chloride, due to beryllium's diagonal relationship with aluminium.

Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005 is the 2005 version of Nomenclature of Inorganic Chemistry. It is a collection of rules for naming inorganic compounds, as recommended by the International Union of Pure and Applied Chemistry (IUPAC).

<span class="mw-page-title-main">Selenium tetrachloride</span> Chemical compound

Selenium tetrachloride is the inorganic compound composed with the formula SeCl4. This compound exists as yellow to white volatile solid. It is one of two commonly available selenium chlorides, the other example being selenium monochloride, Se2Cl2. SeCl4 is used in the synthesis of other selenium compounds.

<span class="mw-page-title-main">Selenium monochloride</span> Chemical compound

Selenium monochloride or diselenium dichloride is an inorganic compound with the formula Se2Cl2. Although a common name for the compound is selenium monochloride, reflecting its empirical formula, IUPAC does not recommend that name, instead preferring the more descriptive diselenium dichloride.

<span class="mw-page-title-main">Sulfur tetrachloride</span> Chemical compound

Sulfur tetrachloride is an inorganic compound with chemical formula SCl4. It has only been obtained as an unstable pale yellow solid. The corresponding SF4 is a stable, useful reagent.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

<span class="mw-page-title-main">Lead(IV) chloride</span> Chemical compound

Lead tetrachloride, also known as lead(IV) chloride, has the molecular formula PbCl4. It is a yellow, oily liquid which is stable below 0 °C, and decomposes at 50 °C. It has a tetrahedral configuration, with lead as the central atom. The Pb–Cl covalent bonds have been measured to be 247 pm and the bond energy is 243 kJ⋅mol−1.

References

  1. ↑ Jolly, William L.; Maguire, Keith D. (1967). "Sulfur Nitrogen Chlorides". Inorganic Syntheses. Vol. IX. p. 102. doi:10.1002/9780470132401.ch27. ISBN   978-0-470-13240-1.
  2. 1 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.
  4. 1 2 Roesky, H. W. (1971). "The Sulfur–Nitrogen Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. pp. 20–23. ISBN   0-8247-1615-9. LCCN   70-154612.
  5. ↑ Rawson, Jeremy M.; Banister, Arthur J.; Lavender, Ian (1995). "The Chemistry of Dithiadiazolylium and Dithiadiazolyl Rings". Adv. Heterocyc. Chem. 62: 146–147. doi:10.1016/S0065-2725(08)60422-5.
  6. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
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