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
