15.12.

2016

SPINELSTRUCTURE|EXPLANATION|ILLUSTRATIONS|CFSE|ADICHEMISTRY

AdiChemistryHome

COORDINATIONCHEMISTRY
<Isolobalanalogy

HSABTheory>

SPINEL&INVERSESPINELSTRUCTURES
ThespinelshavethegeneralformulaAB2X4.
Where:
AII=adivalentcationlikeMg,Cr,Mn,Fe,Co,Ni,Cu,Zn,Cd,Sn
BIII=atrivalentcationlikeAl,Ga,In,Ti,V,Cr,Mn,Fe,Fe,Co,Ni
X=O,S,Seetc.

Structure of Normal Spinels (AB2O4): The divalent AII ions occupy the tetrahedral voids, whereas the
trivalentBIIIionsoccupytheoctahedralvoidsintheclosepackedarrangementofoxideions.
Anormalspinelcanberepresentedas:(AII) tet (BIII) 2oct O4
E.g.MgAl2O4 (knownasspinel),Mn 3O4,ZnFe2O4,FeCr2O4(chromite)etc.

StructuresofInversespinels(B(AB)O4):TheAIIionsoccupytheoctahedralvoids,whereashalfofBIIIions
occupythetetrahedralvoids.Itcanberepresentedas:(BIII)tet(AIIBIII)octO4
E.g.Fe3O4(ferrite),CoFe2O4,NiFe2O4etc.
Theaboveinversespinelscanalsobewrittenas:
Fe3O4=FeIII(FeIIFeIII)O4
CoFe2O4=FeIII(CoIIFeIII)O4
NiFe2O4=FeIII(NiIIFeIII)O4
The number of octahedral sites occupied may be ordered or random. The random occupationleadstodefected
spinels.
E.g.NiAl2O4forwhichtheformulacanbewrittenas(Al0.75Ni0.25)tet[Ni0.75Al1.25]octaO4.
AnotherdefectedspinelisAl2O3

FACTORSAFFECTINGTHESTRUCTUREOFSPINELS
1)TherelativesizesofAandB:Ingeneral,thesmallercationpreferstooccupythesiteoflowercoordination
i.e.,tetrahedralsite.
However,inthespinel,MgAl2O4itselfthisfactorisoutweighedbygreaterlatticeenergyofsmallercation,Al3+,
whichoccupiestheoctahedralsiteandthusbygivingnormalspinelstructure.Otherwisethe"spinel"willhavethe
http://www.adichemistry.com/inorganic/cochem/spinels/spinelstructures.html

1/3

15.12.2016

SPINELSTRUCTURE|EXPLANATION|ILLUSTRATIONS|CFSE|ADICHEMISTRY

inversespinelstucture!
2) The Madelung constants for the normal and inverse structures: It is observed that the Madelung
constantsaresameforbothnormalandinversespinelsandhencearenotthatmuchimportantinarrivingatthe
structure.
3)LigandFleldStabilizationEnergies:Applicablewhenevertherearetransitionmetalionsandisdiscussed
below.
ThestructuresofspinelsareaffectedbytherelativeLFSEvaluesofmetalions.TheionwithmoreLFSEvalue
inoctahedralgeometrywhencomparedtotheLFSEintetrahedralgeometrytendstooccupyoctahedral
sites.
ThedifferencebetweentheLFSEvaluesinoctahedralandtetrahedralgeometriesisreferredtoasOctahedralSite
StabilizationEnergy(OSSE).
If the BIII ion has more CFSE gain in octahedral site than that of AII ion, a normal spinel is
expected.
Whereas an inverse spinel is formed whenever the divalent AIIionhascomparativelymoreCFSE
gaininoctahedralgeometrythanthetrivalentBIIIion.

SOMEGENERALIZATIONSREGARDINGTHESTRUCTURESOFSPINELS
* A normal spinel structure is assumed if both the divalent and the trivalent metals are non transition metals
sincenoCFSEisinvolved.
* There is a tendency of formation of inverse spinel structure in some cases (notallthecases)whichcontain
transitionmetalions.Thisisbecause,thetransitionmetalionmaygetextrastability(LFSE)inoctahedralgeometry,
prefersoctahedralvoidsovertetrahedralones.
*Thed0highspind5,d10ionshavenopreference between tetrahedral and octahedral coordination since the
LFSEiszero.
*Usuallyd3&d8ionshavestrongestpreferenceforoctahedralgeometry.
*Otherionswithd1,d2,d4,d6,d7,d9toohaveslightlymorepreferenceforoctahedralsymmetry.
*Thatmeans,ifAIIhasd3ord8configurationandtheBIIIionhasconfigurationotherthanthese,thenthe
spinelisinverted.
*IfthedivalentAIIisatransitionmetal(withconfigurationsotherthand0highspind5 &d10)andtheBIIIionis
anontransitionmetal,thereisatendencytoforminversespinel.
ButthereareexceptionslikeFeAl2O4whichhasnormalspinelstructure.
*Abovegeneralizationsarevalidforhighspinsystemsastheoxideionisexpectedtobeaweakfieldligand.
Forexample,Co3+isalowspinsystemeveninpresenceofoxoligandsduetohighchargeontheion.
AII

BIII

Structure

Nontransitionmetal
or
0
d ord5ord10
transitionmetal

Nontransitionmetal

Spinelstructure

Nontransitionmetal
or
0
d ord5ord10
transitionmetal

Atransitionmetal
with
d1ord2ord3ord4or
d6ord7ord8ord9

Spinelstructure

configurations

Atransitionmetal
with

Nontransitionmetal
or
d1ord2ord3ord4or transitionmetawith
d6ord7ord8ord9
d0ord5ord10
configurations
configurations
http://www.adichemistry.com/inorganic/cochem/spinels/spinelstructures.html

Inversespinel

2/3

15.12.2016

SPINELSTRUCTURE|EXPLANATION|ILLUSTRATIONS|CFSE|ADICHEMISTRY

Transitionmetalwith Transitionmetalwith
higherCFSEvalue
lowerCFSEvalue

Inversespinel

EXAMPLESFORSPINELANDINVERSESPINELSTRUCTURES
1)MgAl2O4isanormalspinelsinceboththedivalentandtrivalentionsarenontransitionmetalions.Thereis
noquestionofCFSE.
2)Mn 3O4isanormalspinelsincetheMn 2+ionisahighspind5systemwithzeroLFSE.Whereas,Mn 3+ionis
ahighspind4systemwithconsiderableLFSE.
3) Fe3O4 is an inverse spinel since the Fe(III) ion is a high spin d5 system with zero CFSE. Whereas the
divalentFe(II)isahighspind6systemwithmoreCFSE.
4)NiFe2O4 is again an inverse spinelsincethedivalentNi2+ (a d8 ion) has more CFSE than the trivalent
Fe3+(ad5ion).
5)FeCr2O4isanormalspinelsincethedivalentFe2+isahighspind6ionwithCFSE=4Dqandthetrivalent
Cr3+isahighspind3ionwithCFSE=12Dq.HenceCr3+getsmoreOSSEwhileoccupyingoctahedralsites.
6)Co3O4isanormalspinel.Eveninthepresenceofweakfieldoxoligands,theCo3+isalowspind6ionwith
veryhighCFSE.ItisduetohighchargeonCo3+.HencealltheCo3+ionsoccupytheoctahedralsites.
7) NiAl2O4 show random or defected inverse spinel. The CFSE of NiII is greater in octahedral than
tetrahedral coordination. But Al3+ also has strong preference for octahedral sites due to high lattice energy. This
leads to almost complete randomization of all the cations on all the available sites. Its formula can be written as
(Al0.75Ni0.25)tet[Ni0.75Al1.25]octaO4.

<Isolobalanalogy

HSABTheory>

Author:AdityavardhanVutturi

http://www.adichemistry.com/inorganic/cochem/spinels/spinelstructures.html

3/3