zirconium perchlorate
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| Name = Zirconium perchlorate
| ImageFile = Zr(ClO4)4.svg
| ImageSize = 170
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|Section1={{Chembox Identifiers
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| InChI=1S/4ClHO4.Zr/c4*2-1(3,4)5;/h4*(H,2,3,4,5);/q;;;;+4/p-4
| InChIKey = MQGNWZLWQBTZJR-UHFFFAOYSA-J
| SMILES = [Zr](O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)(O[Cl](=O)(=O)=O)O[Cl](=O)(=O)=O
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|Section2={{Chembox Properties
| Appearance = white crystals,
deliquescent
| Odor =
| Zr=1 | Cl=4 | O=16
| Density =
| Solubility = decomposition
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| MeltingPtC = 96
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| BoilingPt = decomposition
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|Section7={{Chembox Hazards
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|Section8={{Chembox Related
| OtherCations = Titanium perchlorate
Hafnium perchlorate
| OtherAnions = Zirconium nitrate
Zirconyl perchlorate
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Zirconium perchlorate is an inorganic compound with the formula Zr(ClO4)4. It is a hygroscopic colorless solid that sublimes in a vacuum at 70 °C. These properties show that the compound is covalently bonded molecule, rather than a salt.{{cite journal|last1=Babaeva|first1=V. N.|last2=Rosolovskii|first2=V. Ya.|title=Anhydrous zirconium perchlorate|journal=Bulletin of the Academy of Sciences of the USSR Division of Chemical Science|date=March 1977|volume=26|issue=3|pages=445–449|doi=10.1007/BF01179439}} It is an example of a transition metal perchlorate complex.{{cite journal |doi=10.1016/S0010-8545(98)00102-7 |title=Inorganic Perchlorato Complexes |date=1998 |last1=Pascal |first1=Jean-Louis |last2=Favier |first2=Frédéric |journal=Coordination Chemistry Reviews |volume=178-180 |pages=865–902 }}
Synthesis and properties
It can be formed by treating zirconium tetrachloride with dichlorine hexoxide-perchloric acid mixture at −35 °C.
Zirconium perchlorate reacts irreversibly with most organic compounds but is inert towards carbon tetrachloride, chloroformide. With benzene at -10°C, crystals of Zr(ClO4)4•C6H6 are deposited.
Solid zirconium perchlorate undergoes a phase transition around 45 °C before melting between 95.5 and 96.0 °C. Thermolysis near 120 °C gives zirconyl perchlorate. Further heating around 290°C gives form zirconia and chlorine oxides.
Structure
In the gas phase the Zr(ClO4)4 molecule has a D4 symmetry with eightfold square antiprism oxygen coordination. Each perchorate group is bidentate. The chlorine atoms are in a tetrahedral arrangement around the central zirconium.{{cite journal|last1=Lapshina|first1=S.B.|last2=Ermolaeva|first2=L.I.|last3=Girichev|first3=G.V.|last4=Spiridonov|first4=V.P.|last5=Golubinskii|first5=A.V.|title=Electron Diffraction Study of the Molecular Structure of Zirconium Perchlorate in the Gas Phase|journal=Russian Journal of Inorganic Chemistry|date=1999|volume=44|issue=4|pages=485–488}}
In the solid phase, Zr(ClO4)4 crystals are monoclinic with a=12.899, b=13.188, c=7.937 Å, β=107.91°. There are four molecules per unit cell.{{cite journal|last1=Genkina|first1=E.A.|last2=Babaeva|first2=V.P.|last3=Rosolovskij|first3=V.Ya.|title=Molecular and crystal structure of anhydrous zirconium perchlorate|journal=Koordinatsionnaya Khimiya|issn=0132-344X|date=1984|volume=10|issue=10|pages=1415–1419|url=https://inis.iaea.org/search/search.aspx?orig_q=RN:17001696}}
Related substances
Titanium perchlorate and hafnium perchlorate are both known.
Salts of perchloratozirconates and hexaperchloratozirconates have been claimed including the caesium perchloratozirconates CsZr(ClO4)5, Cs2Zr(ClO4)6, and Cs4Zr(ClO4)8.{{cite journal|last1=Krivtsov|first1=N. V.|last2=Babaeva|first2=V. P.|last3=Rosolovskii|first3=V. Ya.|title=A thermochemical study of cesium and nitrile perchloratozirconates|journal=Bulletin of the Academy of Sciences of the USSR Division of Chemical Science|date=April 1990|volume=39|issue=4|pages=817–820|doi=10.1007/BF00960355|s2cid=96641367}}{{cite journal|last1=Babaeva|first1=V. P.|last2=Rosolovski|first2=V. Ya.|title=Synthesis and Properties of cesium perchloratozirconates|journal=Zhurnal Neorganicheskoj Khimii|date=1978|volume=23|issue=4|pages=955–959}}
Zirconyl perchlorates have been claimed in older literature.{{cite journal|last1=Murthy|first1=P. Rama|last2=Patel|first2=C. C.|title=Zirconyl perchlorate|journal=Die Naturwissenschaften|date=1961|volume=48|issue=22|pages=693|doi=10.1007/BF00595937|bibcode=1961NW.....48..693M|s2cid=34179500}}