Number of atoms, molecules or ions bonded to a molecule or crystal
In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central ion/molecule/atom is called a ligand. This number is determined somewhat differently for molecules than for crystals.
For molecules and polyatomic ions the coordination number of an atom is determined by simply counting the other atoms to which it is bonded (by either single or multiple bonds).[1] For example, [Cr(NH3)2Cl2Br2]− has Cr3+ as its central cation, which has a coordination number of 6 and is described as hexacoordinate. The common coordination numbers are 4, 6 and 8.
Molecules, polyatomic ions and coordination complexes
In chemistry, coordination number, defined originally in 1893 by Alfred Werner, is the total number of neighbors of a central atom in a molecule or ion.[1][3] The concept is most commonly applied to coordination complexes.
Simple and commonplace cases
The most common coordination number for d-block transition metal complexes is 6. The coordination number does not distinguish the geometry of such complexes, i.e. octahedral vs trigonal prismatic.
For transition metal complexes, coordination numbers range from 2 (e.g., AuI in Ph3PAuCl) to 9 (e.g., ReVII in [ReH9]2−). Metals in the f-block (the
bidentate nitrate ions as ligands, CeIV and ThIV form the 12-coordinate ions [Ce(NO3)6]2− (ceric ammonium nitrate) and [Th(NO3)6]2−. When the surrounding ligands are much smaller than the central atom, even higher coordination numbers may be possible. One computational chemistry study predicted a particularly stable PbHe2+ 15 ion composed of a central lead ion coordinated with no fewer than 15 helium atoms.[4] Among the Frank–Kasper phases, the packing of metallic atoms can give coordination numbers of up to 16.[5] At the opposite extreme, steric shielding can give rise to unusually low coordination numbers. An extremely rare instance of a metal adopting a coordination number of 1 occurs in the terphenyl-based arylthallium(I) complex 2,6-Tipp2C6H3Tl, where Tipp is the 2,4,6-triisopropylphenyl group.[6]
Polyhapto ligands
Coordination numbers become ambiguous when dealing with polyhapto ligands.
For π-electron ligands such as the
cyclooctatetraenide ion [C8H8]2−, the number of adjacent atoms in the π-electron system that bind to the central atom is termed the hapticity.[7] In ferrocene the hapticity, η, of each cyclopentadienide anion is five, Fe(η5-C5H5)2. Various ways exist for assigning the contribution made to the coordination number of the central iron atom by each cyclopentadienide ligand. The contribution could be assigned as one since there is one ligand, or as five since there are five neighbouring atoms, or as three since there are three electron pairs involved. Normally the count of electron pairs is taken.[8]
Surfaces and reconstruction
The coordination numbers are well defined for atoms in the interior of a
crystal lattice: one counts the nearest neighbors in all directions. The number of neighbors of an interior atom is termed the bulk coordination number. For surfaces, the number of neighbors is more limited, so the surface coordination number is smaller than the bulk coordination number. Often the surface coordination number is unknown or variable.[9] The surface coordination number is also dependent on the Miller indices of the surface. In a body-centered cubic (BCC) crystal, the bulk coordination number is 8, whereas, for the (100) surface, the surface coordination number is 4.[10]
Case studies
A common way to determine the coordination number of an atom is by X-ray crystallography. Related techniques include neutron or electron diffraction.[11] The coordination number of an atom can be determined straightforwardly by counting nearest neighbors.
α-Aluminium has a regular cubic close packed structure,
fcc, where each aluminium atom has 12 nearest neighbors, 6 in the same plane and 3 above and below and the coordination polyhedron is a cuboctahedron. α-Iron has a body centered cubic
structure where each iron atom has 8 nearest neighbors situated at the corners of a cube.
Two other examples of commonly-encountered chemicals are
where r0 is the rightmost position starting from r = 0 whereon g(r) is approximately zero, r1 is the first minimum. Therefore, it is the area under the first peak of g(r).
The second coordination number is defined similarly:
Alternative definitions for the coordination number can be found in literature, but in essence the main idea is the same. One of those definition are as follows: Denoting the position of the first peak as rp,
The first coordination shell is the spherical shell with radius between r0 and r1 around the central particle under investigation.[20][21]