Lect.
6
Crystal Chemistry and
Structure Types
Lect. 6-1
Structure Types of
1. AX
2. AX2 & A2X
3. Oxides
4. Hydroxides
5. Oxyanions
AX Structure
• We start our survey of simple ionic survey with
those structures having equal numbers of cation
and anions.
• This stoichiometery means that the absolute
valence of the cation and anion are the same and,
conversely, implies that the coordination number
of the cation must equal the coordination number
of the anion.
CN(A) = CN(X)
Size of Atoms and Ions
see Ch. 3-1
see Ch. 3-1
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Klein, p. 73
AX Structure
A) CN = 8: The
"CsCl" structure
based on a simple
cubic (SC)
arrangement of anions
all the CN=8 (cubic)
sites are filled the
Cs(Cl)8 cubes share
faces. CsCl structure:
Simple cubic (SC) packing of Cl-
All CN(8) sites filled (face-sharing)
Structural Classification AnXm Structures
of Minerals
(Lima-de-Faria) CCP HCP SC
CN=4
CN=6 CN=8
AX Structure
Classification by Lima-de-Faria
CsCl (AcbXsc) structure
• RA/Rx > 0.73
• Larger cation (X) with
1+ charge
ഥ
• P4/m𝟑2/m
• CN ratio of A : X = 8 : 8
Ex) CsCl (RA/Rx=0.92), CsBr (0.86), NH4Cl (0.79), CsI (0.76)
AX Structure
B) CN = 6: The
"NaCl", structure.
Also commonly
called the “Halite“
based on a CCP
arrangement of anions,
which corresponds to
an FCC unit cell alkali halides with radius ratios up to RbCl
the Na(Cl)6 octahedra alkaline earth oxides, including MgO
(periclase)
share edges Some transition metal oxides, including
FeO (Wustite)
The CCP anion layers are oriented perpendicular to the
cube body diagonal
AX Structure
Classification by Lima-de-Faria
NaCl (AoXc) structure
• RA/Rx = 0.73 ~ 0.41
• Strong ionic bonding
character
ഥ
• F4/m𝟑2/m
• CN ratio of A : X = 6 : 6
• However, factors other than the
radius ratio also play a role in the
formation of the crystal structure.
Ex) NaF (RA/Rx=0.73), CCl (0.73), KBr (0.68), PbS (0.65), LiF2 (0.57),
NaCl (0.54), NaBr (0.50), FeO (0.53), AgF (0.95)
AX Structure
Classification by Lima-de-Faria
NiAs (AoXh) structure
• RA/Rx = 0.73 ~ 0.41
• Strong metallic bonding
character
• P63/m2/m2/c
• CN ratio of A : X = 6 : 6
Ex) NiS, FeS,
CoS, Vs, Sn, Pb,
As, Sb, Bi, Se, Te,
Transition metals..
CsCl NaCl NiAs
(Face sharing) (Edge sharing) (Face sharing)
AX Structure
C) CN = 4; The "ZnS" structure.
• sphalerite and wurtzite are polymorphs of zinc sulfide.
섬아연석 섬유아연석
• These structures differ in the packing of the anion (S2-).
sphalerite: CCP
wurtzite: HCP
• However, they are both composed of a network of
corner-linked tetrahedra that results from filling all the
up-ward pointing tetrahdral sites between the anions.
Ex) sphalerite (AtXc): CuCl, CuI, BeS, ZnS, CdS, CdSe, CdTe, AlSb, GaAs
wurtzite (AtXh): BeO, ZnO, CdS
AX Structure
Sphalerite (ZnS) structure,
• Zn occupies all upward-pointing tetrahedral.
• CCP array of S
A
oblique view side view
Wurtzite (ZnS) structure,
• Zn occupies all upward-pointing tetrahedral.
• HCP array of S
oblique view side view
diamond (C, carbon) structure sphalerite (ZnS) structure
ഥ2/m
F41/d𝟑 ഥ3m
F𝟒
Frye (1974) Modern Mineralogy. Prentice Hall, p. 54
see Ch. 5-5
Glide plane (g)
AX Structure Classification by Lima-de-Faria
Spalerlite (AtXc) vs. Wurtzite (AtXh)
• RA/Rx = 0.22 ~ 0.41
• Strong covalent bonding character: Face sharing of
ഥ3m tetrahedron
• F𝟒 vs. P63mc
• CN ratio of A : X = 4 : 4
strong hybridized orbital (sp3)
diamond spalerlite
wurtzite
AX2 Structure
• Structures for minerals with 1 : 2 stoichiometric
ratio of cation : anions.
• valence of A must be twice the valence of the
anion. Conversely, the CN of A must also be
twice the CN of the anion (X).
• As for the AX structures, we will sort these by
the CN of the cation:
AX2 Structure
A) CN = 8: The
"CaF2" fluorite
형석
structure
• anions in a simple cubic
(SC) array
• cations fill one-half the
cubic sites (CN=8)
• anion CN = 4.
• cation polyhedra (cubes)
share edges.
• Unit cell view: Ca are in an FCC arrangement. One Ca is
shown with half its coordination shell. The other four F
coordinated to this Ca are in the adjacent cell to the right.
AX2 Structure
Classification by Lima-de-Faria
CaF2 (AcbX2sc) structure
• RA/Rx > 0.73
ഥ2/m
• F4/m𝟑
• CN ratio of A : X = 8 : 4
• Face sharing of vacant cubic
→ minimum repulsion
Ex) CaF2, SrF2, BaF2, CuF2, CdF2,
SrCl2, BaCl2
general unit cell of fluorite
Polyhedral representation of the fluorite structure
• Face sharing
of vacant
cubic
• Edge sharing
of occupied
cubic
→ minimum
repulsion
AX2 Structure
• B) CN = 6: The
"TiO2" rutile structure
금홍석
(polymorphs: anatase & brookite)
• anions are in an approximately
HCP array
• cations occur as chains of edge-
sharing octahedra
• chains are connected via corners.
• chains are formed by filling one-
half the octahedral sites in a HCP
sheet.
AX2 Structure
"TiO2" (AoXh2) structure
• RA/Rx = 0.73 ~ 0.41
• P42/m21/n2/m
• CN ratio of A : X = 6 : 3
Source: http://www.fangyuan-tio2.com/titanium-iv-oxide-titania-titanium-
dioxide-structure.html
Rutile (TiO2) structure:
Chains of edge-shared octahedra
cross-linked by shared corners
Corresponds to filling one-half A
the octahedral voids in an HCP
array. B
Occupied sites alternate between
layers.
A
Side-view: chain of edge-shared octahedra
HCP array, all octahedral
sites filled = sheet of
edge-shared octahedra
HCP array, one-half of
the octahedral sites
occupied.
Chains of edge-shared
octahedra
Ex) Classify the two minerals using Lima-de-Faria notation.
Cl-, I-
octa 자리
CdCl2 CdI2
A2X Structure
edge sharing
Antistructure
CCP (i.e., antifluorite structure)
At2Xc structure is
preferred
because the electrostatic
repulsion between
positive ions does not
increase the potential
energy of the crystal.
Face sharing
Ex) Li2O, Li2S, Na2O
HCP general unit cell of fluorite (CaF2)
(AcbX2sc)
