Tin(IV) chloride

Tin(IV) chloride
Anhydrous Tin(IV) chloride
Tin(IV) chloride pentahydrate
Names
IUPAC names
Tetrachlorostannane
Tin tetrachloride
Tin(IV) chloride
Other names
Stannic chloride
Identifiers
7646-78-8 Yes
10026-06-9 (pentahydrate)
ChemSpider 22707 Yes
EC number 231-588-9
Jmol-3D images Image
PubChem 24287
RTECS number XP8750000
UN number 1827
Properties
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)
decomposes (anhydrous)
very soluble (pentahydrate)
Solubility soluble in alcohol, benzene, toluene, chloroform, acetone, kerosene, CCl4, methanol, gasoline, CS2
1.512
Structure
Crystal structure monoclinic (P21/c)
Hazards
MSDS ICSC 0953
EU Index 050-001-00-5
EU classification Corrosive (C)
R-phrases R34, R52/53
S-phrases (S1/2), S7/8, S26, S45, S61
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazards (white): no codeNFPA 704 four-colored diamond
0
3
1
Related compounds
Other anions
 Tin(IV) fluoride
Tin(IV) bromide
Tin(IV) iodide
Other cations
 Carbon tetrachloride
Silicon tetrachloride
Germanium tetrachloride
Tin(II) chloride
Lead(IV) chloride
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride is a chemical compound with the formula SnCl4. At room temperature it is a colourless liquid, which fumes on contact with air, giving a stinging odor. It was first discovered by Andreas Libavius (1550–1616) and was known as "spiritus fumans libavii".[1]

Preparation

It is prepared from reaction of chlorine gas with elemental tin.

Sn + 2 Cl2 → SnCl4

Structure

Tin(IV) chloride solidifies at −33 °C to give monoclinic crystals with the P21/c space group; making it isostructural to solidified SnBr4. Within this the molecules adopt near perfect tetrahedral symmetry with average Sn–Cl distances of 227.9(3) pm.[2]

Reactions

When mixed with a small amount of water a semi-solid crystalline mass of the pentahydrate, SnCl4.5H2O is formed.[1] This was formerly known as butter of tin.[1] This compound has been shown to be best described as [SnCl4(H2O)2].3H2O, consisting of cis-[SnCl4(H2O)2] units linked in chains with three hydrate water molecules.[3] Several lower hydrates have also been characterised.[4]

With hydrochloric acid the complex [SnCl6]2− is formed making the so-called hexachlorostannic acid.[1]

Anhydrous tin(IV) chloride is a strong Lewis acid and complexes with e.g. ammonia, phosphine and phosphorus pentachloride are known.[1] SnCl4 is used in Friedel-Crafts reactions as a catalyst for homogeneous alkylation and cyclisation.[1]

With Grignard reagents tetraalkyltin compounds can be prepared:[5]

SnCl4 + RMgCl → SnR4 + MgCl2

Uses

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 substituted for by a mixture of silicon tetrachloride and titanium tetrachloride near the end of the War due to shortages of tin.[6] It is also used in the glass container industry for making an external coating containing tin(IV) oxide which toughens the glass. It is a starting material for organotin compounds.

Stannic chloride is used in chemical reactions with fuming (90%) nitric acid for the selective nitration of activated aromatic rings in the presence of unactivated ones.[7]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5
  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; Reid, Gillian; Webster, Michael (2004). "Hydrates of tin tetrachloride". Acta Crystallographica Section C Crystal Structure Communications 60 (4): i47–i49. doi:10.1107/S0108270104005633.
  5. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0080379419.
  6. ↑ Fries, Amos A. (2008). Chemical Warfare. Read. pp. 148–49, 407. ISBN 1-4437-3840-9..
  7. ↑ 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.

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