Tin(IV) chloride

Tin(IV) chloride
Tin (IV) chloride Anhydrous Tin(IV) chloride	Tin(IV) chloride pentahydrate.jpg Tin(IV) chloride pentahydrate
Names
	IUPAC names Tetrachlorostannane; Tin tetrachloride; Tin(IV) chloride
	Other names Stannic chloride
Identifiers
CAS Number	7646-78-8 ; 10026-06-9 (pentahydrate) ;
3D model (JSmol)	anhydrous: Interactive image; pentahydrate: Interactive image;
ChemSpider	22707 ;
ECHA InfoCard	100.028.717
EC Number	231-588-9;
PubChem CID	24287;
RTECS number	XP8750000;
UNII	67H76LFL3V ;
UN number	1827
CompTox Dashboard (EPA)	DTXSID1029679 ;
	InChI InChI=1S/4ClH.Sn/h41H;/q;;;;+4/p-4 Key: HPGGPRDJHPYFRM-UHFFFAOYSA-J ; InChI=1/4ClH.Sn/h41H;/q;;;;+4/p-4 Key: HPGGPRDJHPYFRM-XBHQNQODAC;
	SMILES anhydrous: Cl[Sn](Cl)(Cl)Cl; pentahydrate: Cl[Sn-2](Cl)(Cl)([OH2+])([OH2+])Cl.O.O.O;
Properties
Chemical formula	SnCl4
Molar mass	260.50 g/mol (anhydrous) ; 350.60 g/mol (pentahydrate)
Appearance	Colorless fuming liquid
Odor	Acrid
Density	2.226 g/cm3 (anhydrous) ; 2.04 g/cm3 (pentahydrate)
Melting point	−34.07 °C (−29.33 °F; 239.08 K) (anhydrous) ; 56 °C (133 °F; 329 K) (pentahydrate)
Boiling point	114.15 °C (237.47 °F; 387.30 K)
Solubility in water	hydrolysis,very hygroscopic (anhydrous) ; very soluble (pentahydrate)
Solubility	soluble in alcohol, benzene, toluene, chloroform, acetone, kerosene, CCl4, methanol, gasoline, CS2
Vapor pressure	2.4 kPa
Magnetic susceptibility (χ)	−115·10−6 cm3/mol
Refractive index (nD)	1.512
Structure
Crystal structure	monoclinic (P21/c)
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H314, H412
Precautionary statements	P260, P264, P273, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P405, P501
NFPA 704 (fire diamond)	3 0 1
Safety data sheet (SDS)	ICSC 0953
Related compounds
Other anions	Tin(IV) fluoride; Tin(IV) bromide; Tin(IV) iodide
Other cations	Carbon tetrachloride; Silicon tetrachloride; Germanium tetrachloride; Lead(IV) chloride
Related compounds	Tin(II) chloride
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound of tin and chlorine with the formula SnCl₄. It is a colorless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds.^[1] It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

Preparation

It is prepared from reaction of chlorine gas with tin at 115 °C (239 °F):

Sn + 2Cl
₂ → SnCl
₄

Structure

Anhydrous tin(IV) chloride solidifies at −33 °C to give monoclinic crystals with the P21/c space group. It is isostructural with SnBr₄. The molecules adopt near-perfect tetrahedral symmetry with average Sn–Cl distances of 227.9(3) pm.^[2]

Space-filling model of anhydrous SnCl₄.

Structure of solid SnCl₄.

Reactions

Tin(IV) chloride is well known as a Lewis acid. Thus it forms hydrates. The pentahydrate SnCl₄·5H₂O was formerly known as butter of tin. They all consist of [SnCl₄(H₂O)₂] molecules together with varying amounts of water of crystallization. The additional water molecules link together the molecules of [SnCl₄(H₂O)₂] through hydrogen bonds.^[3] Although the pentahydrate is the most common hydrate, lower hydrates have also been characterised.^[4]

Aside from water, other Lewis bases form adducts with SnCl₄. These include ammonia and organophosphines. The complex [SnCl₆]²⁻ is formed with hydrochloric acid making hexachlorostannic acid.^[1]

Applications

Precursor to organotin compounds

Anhydrous tin(IV) chloride is a major precursor in organotin chemistry. Upon treatment with Grignard reagents, tin(IV) chloride gives tetraalkyltin compounds:^[5]

SnCl₄ + 4 RMgCl → SnR₄ + 4 MgCl₂

Anhydrous tin(IV) chloride reacts with tetraorganotin compounds in redistribution reactions:

SnCl₄ + SnR₄ → 2 SnCl₂R₂

These organotin halides are useful precursors to catalysts (e.g., dibutyltin dilaurate) and polymer stabilizers.^[6]

Organic synthesis

SnCl₄ is used in Friedel–Crafts reactions as a Lewis acid catalyst.^[1] For example, the acetylation of thiophene to give 2-acetylthiophene is promoted by tin(IV) chloride.^[7] Similarly, tin(IV) chloride is useful for the nitrations.^[8]

Safety

Stannic chloride was used as a chemical weapon in World War I, as it formed an irritating (but non-deadly) dense smoke on contact with air. It was supplanted by a mixture of silicon tetrachloride and titanium tetrachloride near the end of the war due to shortages of tin.^[9]

References

^ ^a ^b ^c Egon Wiberg, Nils Wiberg, Arnold Frederick Holleman (2001). Inorganic Chemistry. Elsevier. ISBN 0-12-352651-5.{{cite book}}: CS1 maint: multiple names: authors list (link)
^ Reuter, Hans; Pawlak, Rüdiger (April 2000). "Die Molekül- und Kristallstruktur von Zinn(IV)-chlorid". Zeitschrift für anorganische und allgemeine Chemie (in German). 626 (4): 925–929. doi:10.1002/(SICI)1521-3749(200004)626:4<925::AID-ZAAC925>3.0.CO;2-R.
^ Barnes, John C.; Sampson, Hazel A.; Weakley, Timothy J. R. (1980). "Structures of di-μ-hydroxobis[aquatrichlorotin(IV)]-1,4-dioxane(1/3), di-μ-hydroxobis[aquatrichlorotin(IV)]-1,8-epoxy-p-menthane(1/4), di-m-hydroxobis[aquatribromotin(IV)]-1,8-epoxy-p-menthane(1/4), di-μ-hydroxobis[aquatrichlorotin(IV)], and cis-diaquatetrachlorotin(IV)". J. Chem. Soc., Dalton Trans. (6): 949. doi:10.1039/DT9800000949.
^ Genge, Anthony R. J.; Levason, William; Patel, Rina; et al. (2004). "Hydrates of tin tetrachloride". Acta Crystallographica Section C. 60 (4): i47–i49. doi:10.1107/S0108270104005633. PMID 15071197.
^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
^ G. G. Graf "Tin, Tin Alloys, and Tin Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH, Weinheim. doi:10.1002/14356007.a27_049
^ John R. Johnson, G. E. May (1938). "2-Acetothienone". Organic Syntheses. 18: 1. doi:10.15227/orgsyn.018.0001.
^ Thurston, David E.; Murty, Varanasi S.; Langley, David R.; Jones, Gary B. (1990). "O-Debenzylation of a Pyrrolo[2,1-c][1,4]benzodiazepine in the Presence of a Carbinolamine Functionality: Synthesis of DC-81". Synthesis. 1990: 81–84. doi:10.1055/s-1990-26795. S2CID 98109571.
^ Fries, Amos A. (2008). Chemical Warfare. Read. pp. 148–49, 407. ISBN 978-1-4437-3840-8..

External links

International Chemical Safety Card 0953
tinchemical.com/products (industrial uses) at the Wayback Machine (archived 2005-02-28)

[Wiberg&Holleman-1] Egon Wiberg, Nils Wiberg, Arnold Frederick Holleman (2001). Inorganic Chemistry. Elsevier. ISBN 0-12-352651-5.{{cite book}}: CS1 maint: multiple names: authors list (link)

[2] Reuter, Hans; Pawlak, Rüdiger (April 2000). "Die Molekül- und Kristallstruktur von Zinn(IV)-chlorid". Zeitschrift für anorganische und allgemeine Chemie (in German). 626 (4): 925–929. doi:10.1002/(SICI)1521-3749(200004)626:4<925::AID-ZAAC925>3.0.CO;2-R.

[3] Barnes, John C.; Sampson, Hazel A.; Weakley, Timothy J. R. (1980). "Structures of di-μ-hydroxobis[aquatrichlorotin(IV)]-1,4-dioxane(1/3), di-μ-hydroxobis[aquatrichlorotin(IV)]-1,8-epoxy-p-menthane(1/4), di-m-hydroxobis[aquatribromotin(IV)]-1,8-epoxy-p-menthane(1/4), di-μ-hydroxobis[aquatrichlorotin(IV)], and cis-diaquatetrachlorotin(IV)". J. Chem. Soc., Dalton Trans. (6): 949. doi:10.1039/DT9800000949.

[4] Genge, Anthony R. J.; Levason, William; Patel, Rina; et al. (2004). "Hydrates of tin tetrachloride". Acta Crystallographica Section C. 60 (4): i47–i49. doi:10.1107/S0108270104005633. PMID 15071197.

[Greenwood-5] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.

[Ullmann-6] G. G. Graf "Tin, Tin Alloys, and Tin Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH, Weinheim. doi:10.1002/14356007.a27_049

[7] John R. Johnson, G. E. May (1938). "2-Acetothienone". Organic Syntheses. 18: 1. doi:10.15227/orgsyn.018.0001.

[8] Thurston, David E.; Murty, Varanasi S.; Langley, David R.; Jones, Gary B. (1990). "O-Debenzylation of a Pyrrolo[2,1-c][1,4]benzodiazepine in the Presence of a Carbinolamine Functionality: Synthesis of DC-81". Synthesis. 1990: 81–84. doi:10.1055/s-1990-26795. S2CID 98109571.

[9] Fries, Amos A. (2008). Chemical Warfare. Read. pp. 148–49, 407. ISBN 978-1-4437-3840-8..

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