The rock-salt structure

Alkali halides that crystallize with the "rock-salt" structure exemplified by sodium chloride can be regarded either as a FCC structure of one kind of ion in which the octahedral holes are occupied by ions of opposite charge, or as two interpenetrating FCC lattices made up of the two kinds of ions. The two shaded octahedra illustrate the identical coordination of the two kinds of ions; each atom or ion of a given kind is surrounded by six of the opposite kind, resulting in a coordination expressed as (6:6).

How many NaCl units are contained in the unit cell? If we ignore the atoms that were placed outside the cell in order to construct the octahedra, you should be able to count fourteen "orange" atoms and thirteen "blue" ones. But many of these are shared with adjacent unit cells.

An atom at the corner of the cube is shared by eight adjacent cubes, and thus makes a 1/8 contribution to any one cell. Similarly, the center of an edge is common to four other cells, and an atom centered in a face is shared with two cells. Taking all this into consideration, you should be able to confirm the following tally showing that there are four AB units in a unit cell of this kind.

If we take into consideration the actual sizes of the ions (Na⁺ = 116 pm, Cl^– = 167 pm), it is apparent that neither ion will fit into the octahedral holes with a CCP lattice composed of the other ion, so the actual structure of NaCl is somewhat expanded beyond the close-packed model.

The space-filling model on the right [source] depicts a face-centered cubic unit cell of chloride ions (purple), with the sodium ions (green) occupying the octahedral sites.

The zinc-blende structure: using some tetrahedral holes

Since there are two tetrahedral sites for every atom in a close-packed lattice, we can have binary compounds of 1:1 or 1:2 stoichiometry depending on whether half or all of the tetrahedral holes are occupied.

Zinc-blende is the mineralogical name for zinc sulfide, ZnS. An impure form known assphalerite is the major ore from which zinc is obtained.

This structure consists essentially of a FCC (CCP) lattice of sulfur atoms (orange) (equivalent to the lattice of chloride ions in NaCl) in which zinc ions (green) occupy half of the tetrahedral sites. As with any FCC lattice, there are four atoms of sulfur per unit cell, and the the four zinc atoms are totally contained in the unit cell.

Each atom in this structure has four nearest neighbors, and is thus tetrahedrally coordinated.

It is interesting to note that if all the atoms are replaced with carbon, this would correspond to the diamond structure.

The fluorite structure: all tetrahedral sites occupied

Fluorite, CaF₂, having twice as many ions of fluoride as of calcium, makes use of all eight tetrahedral holes in the CPP lattice of calcium ions (orange) depicted here. To help you understand this structure, we have shown some of the octahedral sites in the next cell on the right; you can see that the calcium ion at A is surrounded by eight fluoride ions, and this is of course the case for all of the calcium sites. Since each fluoride ion has four nearest-neighbor calcium ions, the coordination in this structure is described as (8:4).

Although the radii of the two ions (F^–= 117 pm, Ca²⁺ = 126 pm does not allow true close packing, they are similar enough that one could just as well describe the structure as a FCC lattice of fluoride ions with calcium ions in the octahedral holes.

Date: 2016-01-03; view: 2026