Crystalline Solids

When cooled slowly, atomic and molecular building blocks can

assemble into well-ordered minimum-energy structures: Crystals
Examples

CuSO4 5H2O

Ag

Quartz SiO2

Cu

Cholesterol

MnB(OH)3

Pharmaceutical Example: ROY

5-Methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile
N

O
N

C
H
N

S
CH3

6 polymorphic forms
more generally

Comparison: Amorphous solids

Tar, molten glass, molten plastics,
and molten butter, consist of large
molecules or a mixture of
molecules that cannot move
readily. As the temperature is
lowered, their molecules move
more and more slowly and finally
stop in random positions. The
resulting materials are called
amorphous solids or glasses.
Such solids lack an ordered
internal structure. Common
examples include candle wax,
butter, glass, and plastics.

Crystalline Solids
Metallic crystals
Ag, Cu: metallic bonds, soft to hard, low to high melting
points, good conductors of heat and electricity
Crystals of packed molecules
CH4, cholesterol: dispersion, dipole-dipole, H-bonds,
soft, low melting, poor conductors
Ionic crystals
NaCl, CuSO4: electrostatic attraction, hard, brittle, poor
conductors of heat and electricity
Network covalent crystals
Diamond, -SiO2-: hard, high melting, poor electrical
conductors, poor to excellent heat conduction

Definitions
Unit Cell:

The smallest repeating unit in a three dimensional

structure (lattice)

Different geometric arrangements

depending on the crystal type
Characterized by a coordination
number (number of nearest neighbors)
Bonding

and a lattice parameter, a (edge length)

Atomic radius -- Bulk density

The crystal lattice and the unit cell

The unit cell is the

minimum repeating
unit necessary to
describe the crystal.

Definitions
Crystal Systems:

Arrangements for stacking spheres, each one

characterized by a packing efficiency (percentage of
total volume occupied by spheres)

Cubic Systems
a=b=c, =90
CN
6

PE
54%

Body-centered Cubic (BCC)

68%

Face-centered Cubic (FCC)

12

74%

Simple Cubic (SC)

Crystal Systems
There are 7 types of crystal systems, 14 units cells, but we will look at
cubic and the hexagonal systems.
1) Simple cubic unit cell
8 atoms define corners atoms touch along edges, but not along
diagonal
Coordination # = 6. 4 in layer, 1 above, 1 below
1 atom/unit cell (1/8 8 atoms)
2) Body-centered cubic unit cell
8 atoms define corners plus one in center atoms touch central atom,
not each other
Coordination # = 8. 4 above and 4 below.
2 atoms/unit cell (1/8 8 atoms + 1 atom in center)
3) Face-centered cubic unit cell
8 atoms define corners plus 6 in center of each face Corner atoms
touch face atom, not each other
Coordination # = 12. 4 in layer, 1 above, 1 below, 6 faces
4 atoms/unit cell (1/8 8 crnr atoms + 6 face atoms)

Simple Cubic (SC)

SC lattice and crystal structure
a

Coordination number = 6

SC
a = 2R
Where:

R = atomic radius
a = lattice parameter

Packing fraction = 54%

Body Centered Cubic (BCC)

a
Packing fraction = 68%
Coordination number = 8

BCC
a =

4R
3

Where:

R = atomic radius
a = lattice parameter

Where does this come from?

Cubic Packing - BCC

3a

a
2 a
a

2 a
3a=4R
a=4R/3

Face Centered Cubic (FCC)

A close-packed structure
with a packing fraction of 74%
Coordination number = 12

FCC
4R
a =
2
a = 2R 2
Where:

R = atomic radius
a = lattice parameter

Packing Arrangements
How do these packing arrangements arise?
Start always with a layer of atoms, separated center to center
by the lattice parameter, a.

Then, place a layer on top, over atoms or over spaces.

Thus, for a simple cubic lattice (SC):

The first layer is spaced with a = 2R

Then the second layer is placed with every atom directly atop
the one below
Not a close-packed structure.
Coordination number = 6
(octahedral)
Packing fraction = 54%

For a body-centered cubic lattice (BCC):

The first layer is spaced with

4
a
R
3
Still not a close-packed structure.

Coordination number = 8
(bi-prism)

Packing fraction = 68%

Then, the second layer is placed over the spaces between atoms.
Finally, a third layer lines up directly over the atoms in the first.

The close-packed crystalsystems

Cubic closest packing or face-centered cubic, FCC

Shift every other row in the first layer

to compress packing
Place second layer over triangular spaces
Third layer over gaps that remain
Tilt to find unit cell
A close-packed structure with a packing
fraction of 74%

abcabc

The close-packed crystal systems

Hexagonal closest packing, HCP
Shift every other row in the first layer
to compress packing
Place second layer over triangular spaces
Third layer directly over the atoms of the first
Rhombic unit cell
A close-packed structure with a packing
fraction of 74%
Coordination # = 12

abab

(3 above, 6 in the plane, 3 below)

Packing efficiency
Describes the total volume occupied by atoms in the unit cell.
For a given atom radius, the higher the coordination, the higher the
packing efficiency:
Cell Type
Coordination # Packing
Efficiency
Simple cubic

52%

Body-centered cubic

68%

Face-centered cubic

12

74%

12

74%

aka, (cubic closest packing)

Hexagonal

You can calculate these from simple geometry, like you did in lab, by
relating the unit cell and atomic radius information.
Most metallic elements pack in hexagonal closest packing lattice.
Many ionic compounds are fcc. (NaCl two interspersed fcc lattices.)

Packing of spheres.

simple cubic
(52% packing efficiency)
body-centered cubic
(68% packing efficiency)

layer a
hexagonal
closest
packing

layer a

layer b
cubicclosest
packing

layer c

closest packing of first

and second layers

abab

abcabc

The structures of simple ionic

compounds
In simple ionic structures
space is filled as compactly as possible
ions of one charge are surrounded by as many ions as
possible of the opposite charge
positive and negative ions touch
Ionic structures are determined by two principal factors
the relative sizes of the ions
the ratio of the numbers of positive and negative ions in
the compound

The structures of simple ionic

compounds
In simple ionic structures we usually find the anions, which
are normally larger than the cations, arranged in a simple
cubic or a closest packed array.
Relatively small cations occupy tetrahedral holes
Larger cations occupy octahedral holes
Even larger cations occupy larger cubic holes in a
simple cubic array of anions

Holes

Tetrahedral
holes

Octahedral hole

Cubic hole

The CsCl structure

Cl ion
Cs+ ion

The CsCl unit cell

CsCl: Cs+ ions occupy all
the cubic holes in a
simple cubic array of Cl
ions.

A unit cell contains 1 Cs+

ion and 1 Cl ion. Ions
touch along the body
diagonal.

The CaF2 structure

F ion

Ca2+ ion

The CaF2 unit cell

CaF2: F ions occupy all
the cubic holes in a
simple cubic array of Ca2+
ions.

The fluorite (CaF2) structure.

A unit cell contains 4 Ca2+ ions and 8 F

ions. Ions touch along the body diagonal.
F- ions are tetrahedral coordinated, Ca2+ are octahedrally coordinated.

The NaCl structure

Cl ion
Na+ ion

The NaCl unit cell

The NaCl unit cell

The sodium chloride structure.

expanded view

space-filling

A unit cell contains 4 Na+ ions and 4 Cl ions.

Ions touch along the cell edge

The ZnS, zinc blende, structure

S2 ion

Zn2+ ion

The zinc blende unit cell

A unit cell contains 4 Zn2+ ions and 4 S2 ions. Ions

touch along the body diagonal.
Zn2+ ions fit in tetrahedral holes