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Coordination Number

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Coordination Number

Anhydrous and hydrated cobalt chloride have very different colors

What makes the colors different?

The two cobalt salts pictured above both contain Co 2+ cations.  The difference in color is due to the species surrounding the cobalt ion.  The presence of water molecules in the coordination sphere around the central cobalt ion changes the distances among species and the color of the material.

Coordination Number

The coordination number is the number of ions that immediately surround an ion of the opposite charge within a crystal lattice.  If you examine the figure below, you will see that there are six chloride ions immediately surrounding a single sodium ion.  The coordination number of sodium is 6.  Likewise, six sodium ions immediately surround each chloride ions, making the coordination number of chloride also equal to 6.  Because the formula unit of sodium chloride displays a 1:1 ratio between the ions, the coordination numbers must be the same.

Lattice structure for sodium chloride

Lattice structure for sodium chloride. The blue balls represent the sodium ions and the green balls represent the chloride ions

The formula unit for cesium chloride is CsCl, also a 1:1 ratio.  However, as shown in the figure below, the coordination numbers are not 6 as in NaCl.  The center ion is the Cs + ion and is surrounded by the eight Cl ions at the corners of the cube.  Each Cl ion is also surrounded by eight Cs + ions.  The coordination numbers in this type of crystal are both 8.  CsCl and NaCl do not adopt identical crystal packing arrangements because the Cs + ion is considerably larger than the Na + ion.

Lattice structure for cesium chloride

In a cesium chloride crystal, the cesium ion (orange) occupies the center, while the chloride ions (green) occupy each corner of the cube. The coordination number for both ions is 8.

Another type of crystal is illustrated by titanium(IV) oxide, TiO 2 , which is commonly known as rutile.  The rutile crystal is shown below.

Lattice structure for titanium chloride

Titanium(IV) oxide forms tetragonal crystals. The coordination number of the Ti 4+ ions (gray) is 6, while the coordination number of the O 2 ions (red) is 3.

The gray Ti 4+ ions are surrounded by six red O 2− ions.  The O 2− ions are surrounded by three Ti 4+ ions.  The coordination of the titanium(IV) cation is 6, which is twice the coordination number of the oxide anion, which is 3.  This fits with the formula unit of TiO 2 , since there are twice as many O 2− ions as Ti 4+ ions.

The crystal structure of all ionic compounds must reflect the formula unit.  In a crystal of iron(III) chloride, FeCl 3 , there are three times as many chloride ions as iron(III) ions.

Lattice structure for iron chloride

Iron(III) chloride. The bluish-gray Fe 3+ ions are surrounded by green Cl - ions.

Summary

  • The coordination number of a compound is determined by the type and number of ions or other species surrounding a central ion.
  • Often the color of a compound is affected by the specific materials coordinated to that central ion.

Practice

Questions

Use the link below to answer the following questions:

http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch12/complex.php

  1. What are the ions or molecules that bind to transition metal ions called?
  2. How many complexes of CoCl 3 can be isolated?
  3. What is a monodentate ligand?
  4. What are the most common coordination numbers?

Review

Questions

  1. What is the coordination number for Na + in NaCl?
  2. What is the coordination number for Cs + ?
  3. Why are the packing arrangements for Na + and Cs + different?

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