Coordination Polyhedra

Consider coordination of anions about a

central cation
Halite
Na
Cl

Cl Cl

Cl
 Coordination Polyhedra
Na
Could do the opposite,
but conventionally Na Cl Na
choose the cation
Can predict the coordination Na

by considering the radius ratio:

RC/RA
Cations are generally smaller than anions so
begin with maximum ratio = 1.0
 Coordination Polyhedra
Radius Ratio: RC/RA = 1.0 (commonly native elements)
Equal sized spheres
Closest Packed
Hexagonal array:
6 nearest neighbors 2 1
in the plane
Note dimples in which
next layer atoms will
settle
Two dimple types:
Type 1 point NE
Type 2 point SW
They are equivalent since
you could rotate the
whole structure 60o and
exchange them
 Closest Packing
Add next layer (red)
Red atoms can only
settle in one
dimple type
Both types are
identical and red 1
atoms could
settle in either
Once first red atom
settles in, can
only fill other
dimples of that
type
In this case filled all
type 2 dimples
 Closest Packing
Third layer ??
Third layer dimples
are now different!
Call layer 1 A sites
Layer 2 = B sites (no
matter which
choice of dimples
is occupied)
Layer 3 can now
occupy A-type site
(directly above
yellow atoms) or
C-type site (above
voids in both A
and B layers)
 Closest Packing
Third layer:
If occupy A-type site
the layer ordering
becomes A-B-A-B
and creates a
hexagonal closest
packed structure
(HCP)

Coordination number
(nearest or touching
neighbors) = 12
6 coplanar
3 above the plane
3 below the plane
 Closest Packing
Third layer:
If occupy A-type site
the layer ordering
becomes A-B-A-B
and creates a
hexagonal closest
packed structure
(HCP)
 Closest Packing
Third layer:
If occupy A-type site
the layer ordering
becomes A-B-A-B
and creates a
hexagonal closest
packed structure
(HCP)
 Closest Packing
Third layer:
If occupy A-type site
the layer ordering
becomes A-B-A-B
and creates a
hexagonal closest
packed structure
(HCP)
 Closest Packing
Third layer:
If occupy A-type site
the layer ordering
becomes A-B-A-B
and creates a
hexagonal closest
packed structure
(HCP)

Note top layer atoms

are directly above
bottom layer atoms
 Closest Packing
Third layer:

Unit cell
 Closest Packing
Third layer:

Unit cell
 Closest Packing
Third layer:

Unit cell
 Closest Packing
Third layer:

View from top shows

hexagonal unit cell
 Closest Packing
Third layer:

View from top shows

hexagonal unit cell
Hexagonal Closest Packing

Click to run animation Case Klein animation

for Mineral Science, John Wiley & Sons
 Closest Packing

Alternatively we could
place the third layer in
the C-type site (above
voids in both A and B
layers)
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
View from the same side
shows the face-
centered cubic unit
cell that results.
A-layer
The atoms are slightly
shrunken to aid in
visualizing the
structure
C-layer

B-layer

A-layer
 Closest Packing
Rotating toward a top
view
 Closest Packing
Rotating toward a top
view
 Closest Packing
You are looking at a top
yellow layer A with a
blue layer C below,
then a red layer B and
a yellow layer A again
at the bottom
Cubic Closest Packing

Click to run animation Case Klein animation

for Mineral Science, John Wiley & Sons
What happens when RC/RA decreases?

The center cation becomes too small for the XII site
(as if a hard-sphere atom model began to rattle in
the XII site) and it drops to the next lower
coordination number (next smaller site).

It will do this even if it is slightly too large for the

next lower site.

It is as though it is better to fit a slightly large

cation into a smaller site than to have one rattle
about in a site that is too large.
Coordination Polyhedra

Click to run animation Case Klein animation

for Mineral Science, John Wiley & Sons
 The next smaller crystal site is:

Body-Centered Cubic
(BCC) with cation
(red) in the center of a
cube

Coordination number is
now 8 (corners of
cube)
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).
Set = 1

What is the RC/RA of that arbitrary

limiting condition?? since will
deal with
ratios

Diagonal length then = 2

 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.
Central Plane = 1 + 2 = 1.732
What is the RC/RA of that
limiting condition??

1.732 = dC + dA

=1
If dA = 1 (arbitrary)
then dC = 0.732

dC/dA = RC/RA
= 0.732/1 = 0.732
= 2
The limits for VIII coordination are thus between 1.0
(when it would by CCP or HCP) and 0.732

Note: BCC is not a = 1 + 2 = 1.732

cosest-packed
oxygen arrangement,
so it may not occur
in all ionic crystal
lattices
=1
(arbitrary)

= 2
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
What is the RC/RA of that
limiting condition??

1.414 = dC + dA
= 2
=1
If dA = 1
then dC = 0.414

dC/dA = RC/RA
= 0.414/1 = 0.414
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
What is the RC/RA of the limiting
condition??

Center-to-corner distance of a
tetrahedron with edges of 1.0
= 0.6124 0.5 0.61
1
RC = 0.612 - 0.5 = 0.1124

RC/RA
= 0.1124/0.5 = 0.225
As RC/RA continues to decrease below the 0.22 the
cation will move to the next lower coordination: III.
The cation moves from the center of the tetrahedron to
the center of an coplanar tetrahedral face of 3 oxygen
atoms
What is the RC/RA of the
limiting condition??

cos 60 = 0.5/y y = 0.577

0.5 y
RC = 0.577 - 0.5 = 0.077 1

RC/RA
= 0.077/0.5 = 0.155
If RC/RA decreases below the 0.15 (a are situation) the
cation will move to the next lower coordination: II.
The cation moves directly between 2 neighboring
oxygen atoms
 Homework Exercise
Use RC/ROxygen and the limits above to determine the
probable coordination of the following elements in
silicate and oxide minerals:

Si+4 Mg2+
Al3+ Ti4+
K+ Ca2+
Fe2+ Na+

Correct RC for cases in which the coordination is not VI (the

standard) and recalculate the ratio