Coordination of Ions

Dr. Stephen Crabtree

September 10, 2018
 Coordination of Ions
• In ionically-bonded
crystals, ions will try to
gather as many
oppositely-charged
ions around itself as
possible

• Geometry of
surrounding ions is
simple polyhedra
(fundamental 3D
shapes)
 Coordination of Ions
• The number of
surrounding anions
(or cations) is the
coordination number

• You can have

multiple Example: Fluorite – CaF2
coordination
numbers in the same Ca2+ [8-fold] F1- [4-fold]
crystalline structure C.N. ratio inverse of
balanced molecule
 1.6

Remember…
Pb2+

1.4

Effective Ionic Radii

1.2

Larger ionic 1

Radius of Cation, in Å
radius as 0.8
Zn2+

number of
surrounding 0.6

ions (the 0.4

coordination
0.2
number)
increases 0
2 4 6 8 10 12 14
Coordination Number
 Ionic Radius Ratio
• You can predict the number of ions surrounding a
cation based on the ratio of ion sizes (Å)

• Radius ratio = Rcation : Ranion = RA / RX

 Ionic Radius Ratio
• Anions must border central cation
• Anions often, but not always, touch each other
 Linear Packing
• Rare packing
arrangement
• Ratio < 0.155
• Requires a very
Linear: CN = 2 small cation, and a
comparably very
large anions
• Ex: (UO2)2+, (NO2)2-
 Trigonal Packing
• Rare packing
arrangement
• Ratio = 0.155 – 0.225
• Anions all border
Trigonal: CN = 3 each other and
central cation
• Ex: (CO3)2-, (NO3)2- ,
(BO3)3-
 Tetrahedral Packing
• Very common packing
arrangement
• Ratio = 0.225 – 0.414
• Anions all border
Tetrahedral: CN = 4
central cation, but not
necessarily each other
as cation size increases
• Ex: (SiO4), ZnS
 Octahedral Packing
• Very common packing
arrangement
• Ratio = 0.414 – 0.732
• Anions all border
Octahedral: CN = 6 central cation, but not
necessarily each other
as cation size increases
• Ex: NaCl, KCl,
 Cubic Packing
• Very common
packing arrangement
• Ratio = 0.732 – 1.000
• Cation approaching
Cubic: CN = 8 the same minimum
size as the anions
• Ex: RbCl, CsCl
 Cuboctahedral Packing
• Rare packing
arrangement,
except in pure
metals
Cuboctohedral: CN = 12 • Ratio = 1.000
• Cation must be
the same size as
the anions
 Hexagonal Closest Packing
• Rare packing
arrangement,
except in pure
metals
• Ratio = 1.000
• All ions or atoms
must be the same
size as each other
Hexagonal Closest
Packing: CN = 12
Hexagonal Closest Packing
• Rare packing
arrangement
• Ratio = 1.000
• All ions or atoms
must be the same
size as each other

Hexagonal Closest
Packing: CN = 12
 Cubic Closest Packing
• Rare packing
arrangement,
except in pure
metals
• Ratio = 1.000
• All ions or atoms
must be the same
Cubic Closest Packing: size as each other
CN = 12
Cubic Closest Packing
• Rare packing
arrangement
• Ratio = 1.000
• All ions or atoms
must be the same
size as each other

Cubic Closest Packing:

CN = 12
 Other Types of Packing
• There are recognized
5-, 7-, 9-, and 10-fold
coordinations
• These unusual
coordinations only
occur in complex,
loosely-packed
structures
 Other Types of Packing
• There are also unusual
rearrangements in 4,
6, and 8-fold
coordination
• These unusual
coordinations only
occur in complex,
loosely-packed
structures
Bonding Coordinated Cells
• When coordinated cells
bond to each other, they
bond at apices and edges
• This keeps cations as far
apart as possible
• Reasons formulated by
Linus Pauling

• Ex: Quartz 4-fold

coordination
 Linus Pauling’s Rules
• Major 20th C. chemist

• Fundamental Rules
published in 1929

• Published textbook in
1939 revolutionized
understanding of
chemical bonds

• Crucial development of
the idea of “orbital
(1901-1994)
hybridization”
 Linus Pauling’s Rules
1. Radius Ratios and Coordination Numbers

2. Electrostatic Valency Principle

3. Corners, Edges, and Faces

4. Polyhedra Distortion

5. Principle of Parsimony
 Linus Pauling’s Rules
1. Radius Ratios and
Coordination
Numbers

A coordination
polyhedron of anions
is formed around
each cation, the
coordination number
of the cation
determined by the
radius ratio.
 Linus Pauling’s Rules
1. Radius Ratios and Coordination Numbers

Radius ratio = Rcation : Ranion = RA / RX

 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

The total strength

of the valency
bonds that reach an
anion is equal to
the charge of that
Ex: NaCl
anion, to balance
Na1+ [CN = 6] Cl1- [CN = 6]
the structure as Contributing charge by each
neutral Cl1- bonding to Na1+ is -(+1/6)
 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

Isodesmic – a
structure in which
all of the bond
strengths are
identical
Ex: NaCl
Examples include Na1+ [CN = 6] Cl1- [CN = 6]
Contributing charge by each
many halides and
Na1+ bonding to Cl1- is -(-1/6)
oxides
 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

Isodesmic – a
structure in which
all of the bond
strengths are
identical
Ex: CaF2
Ex: NaCl, MgO, Ca2+ [CN = 8]F1- [CN = 4]
CaF2 , MgAl2O4 Blends two types of coordination,
but maintains valency proportions
 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

The total strength

of the valency
bonds (e.v.) that
reach an anion is
equal to the charge
Ex: CaF2
of that anion, to
Ca2+ [CN = 8]F1- [CN = 4]
form a neutral
Contributing charge by each F1-
structure. bonding to Ca2+ is -(+2/8) = -1/4
 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

The total strength

of the valency
bonds (e.v.) that
reach an anion is
equal to the charge
Ex: CaF2
of that anion, to
Ca2+ [CN = 8]F1- [CN = 4]
form a neutral
Contributing charge by each Ca2+
structure. bonding to F1- is -(-1/4) = 1/4
 Linus Pauling’s Rules
2. Electrostatic Valency
Principle

Anisodesmic – a
structure in which
anions are more Ex: (CO3)2-
strongly bound to one C4+ [CN = 3]
molecular cation than
any other cations Each O2- contributes
4/3 e.v. to each C4+
Occurs when bonding
to molecular groups Leaves 2/3 e.v. to bond with
other elements, ex: Ca2+
 Linus Pauling’s Rules
2. Electrostatic Valency
Principle

Anisodesmic – a
structure in which
anions are more
strongly bound to one
molecular cation than Only 2/3 e.v. to bond with
any other cations other elements, ex: Ca2+

Occurs when bonding Means the O2- is bonded more

to molecular groups strongly to C than to Ca
 Linus Pauling’s Rules
2. Electrostatic Valency
Principle

Mesodesmic – a
structure in which
anions are equally Ex: (SiO4)4-
strongly bound to one Si4+ [CN = 4]
molecular cation as to
any other cations Each O2- contributes
1 e.v. to each Si4+
Greatest example is
Silicates Leaves 1 e.v. to bond with
other elements, ex: Si, Al, Ca
 Linus Pauling’s Rules
2. Electrostatic Valency
Principle

Mesodesmic – a
structure in which
anions are equally
strongly bound to one
molecular cation as to
any other cations Each O2- contributes
1 e.v. to each Si4+
Greatest example is
Leaves 1 e.v. to bond with
Silicates
other elements, ex: Si, Al, Ca
 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

Ex: Ca3Al2Si3O12 (grossular garnet)

Ca2+ [CN = 8] Al3+ [CN = 6] Si4+ [CN = 4]
Blends three types of coordination with oxygen (O2-)
 Linus Pauling’s Rules
2. Electrostatic
Valency Principle

 
 Linus Pauling’s Rules
3. Corners, Edges,
and Faces

The existence of 1.0

edges and faces
common to two
anion polyhedra
in a coordinated
• Tetrahedra sharing a
structure decreases corner anion
its stability. – Very common
– Very stable
 Linus Pauling’s Rules
3. Corners, Edges,
and Faces

The existence of 0.58

edges and faces
common to two
anion polyhedra
in a coordinated
• Tetrahedra sharing two
structure decreases edge anions
its stability. – Very uncommon
– Very unstable, distorted
 Linus Pauling’s Rules
3. Corners, Edges,
and Faces

The existence of 0.33

edges and faces
common to two
anion polyhedra
in a coordinated
• Tetrahedra sharing
structure decreases three face anions
its stability. – Does not occur in nature
– Completely unstable
 Linus Pauling’s Rules
3. Corners, Edges,
and Faces

The existence of 1.00

edges and faces
common to two
anion polyhedra
in a coordinated • Octahedra sharing a
structure decreases corner anion
its stability. – Very common
– Very stable
 Linus Pauling’s Rules
3. Corners, Edges, 0.71
and Faces

The existence of
edges and faces
common to two
anion polyhedra
in a coordinated • Octahedra sharing two
structure decreases edge anions
its stability. – Common
– Very stable
 Linus Pauling’s Rules
3. Corners, Edges, 0.58 0.71
and Faces

The existence of
edges and faces
common to two
anion polyhedra
in a coordinated • Octahedra sharing three
structure decreases face anions
its stability. – Not uncommon
– Reasonably stable
 Linus Pauling’s Rules
4. Polyhedra Distortion

High valency cations with

small coordination
numbers tend not to
share polyhedral
elements with each other.

When they do, the shared

edges contract, due to
cation-cation repulsion.
 Linus Pauling’s Rules
5. The Principle of
Parsimony:
The number of
different kinds of
constituents in a
crystal is small.
In structures with
complex compositions,
a number of different Ex: Clinoamphibole
ions may occupy the Tetrahedral: Si and Al
same structural site. Octahedral: Mg, Mn, Fe, Al, Ti, Ca, Na
A: Na, K; OH-site: Cl, F, OH
 Linus Pauling’s Rules
5. The Principle of
Parsimony:
The number of
different kinds of
constituents in a
crystal is small.
In structures with
complex compositions,
a number of different Ex: Clinoamphibole
ions may occupy the Tetrahedral: Si and Al
same structural site. Octahedral: Mg, Mn, Fe, Al, Ti, Ca, Na
A: Na, K; OH-site: Cl, F, OH
 Linus Pauling’s Rules
5. The Principle of
Parsimony:
The number of
different kinds of
constituents in a
crystal is small.
In structures with
complex compositions,
a number of different Ex: Clinoamphibole
ions may occupy the Tetrahedral: Si and Al
same structural site. Octahedral: Mg, Mn, Fe, Al, Ti, Ca, Na
A: Na, K; OH-site: Cl, F, OH
 Linus Pauling’s Rules
1. Radius Ratios and Coordination Numbers:

2. Electrostatic Valency Principle

3. Corners, Edges, and Faces

4. Polyhedra Distortion

5. Principle of Parsimony
 Summary: Coordination of Ions
• Ions will try to gather as many
oppositely-bonded ions around
themselves as possible
‒ The number of surrounding anions
(or cations) is the coordination
number (CN)
‒ Geometry of surrounding ions is
simple polyhedra, controlled by
relative sizes of ionic radii
• You can have multiple
coordination numbers in the same
crystalline structure
 Summary: Coordination of Ions
• Fundamental geometries:

Tetrahedral, CN = 4
Linear, CN = 2 Trigonal, CN = 3

Octahedral Cubic Dodecahedral

CN = 6 CN = 8 CN = 12
 Summary: Linus Pauling’s Rules
1. Radius Ratios and Coordination Numbers:

2. Electrostatic Valency Principle

3. Corners, Edges, and Faces

4. Polyhedra Distortion

5. Principle of Parsimony

Any questions??
 Next Time…
• Common Crystal Structure Types…pt. 1