Coordination number

In chemistry and crystallography, the coordination number of a central atom in a molecule or crystal is the number of its nearest neighbours. This number is determined somewhat differently for molecules and for crystals. In chemistry, the emphasis is on bonding structure in molecules or ions and 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). For example, [Cr(NH3)2Cl2Br2]1- has Cr3+ as its central cation, which has a coordination number of 6. However the solid-state structures of crystals often have less clearly defined bonds, so a simpler model is used, in which the atoms are represented by touching spheres. In this model the coordination number of an atom is the number of other atoms that it touches. For an atom in the interior of a crystal lattice, the number of atoms touching the given atom is the bulk coordination number; for an atom at a surface of a crystal, this is the surface coordination number.
The total number of points of attachment to the central element is termed the coordination number and this can vary from 2 to as many as 16, but is usually 6. In simple terms, the coordination number of a complex is influenced by the relative sizes of the metal ion and the ligands and by electronic factors, such as charge which is dependent on the electronic configuration of the metal ion. These competing effects are described by the term ionic potential which is defined as the charge to radius ratio (q/r). Based on this, it can be seen that the bigger the charge on the central ion, the more attraction there will be for negatively charged ligands, however at the same time, the bigger the charge the smaller the ion becomes which then limits the number of groups able to coordinate. Coordination Number 1 Transition metal complexes with the coordination number 1 are rare. In the case of main group elements this coordination number is more common, e.g. in HF, ICl. It can be also observed in the gas phase. Some of the examples known are the copper(I) complex shown here and the analogous Ag(I) complex made by Strhle et al. They used the bulky 2,4,6-(triphenyl)phenyl ligand to prevent aggregation of the molecules Coordination Number 2 This arrangement is not very common for first row transition metal ion complexes and some of the best known examples are for Silver(I). In this case we have a low charge and an ion at the right hand side of the d-block indicating smaller size As in the case of C.N.1 , compounds with the coordination number 2 are very common for main group elements but are less common for transition metal complexes. Two gometry types are possible: Linear and bent. -Linear

This first possibility includes examples in main group chemistry that have this geometry due to the electron pair configuration: No lone pairs (e.g. BeF2 in the gasphase, CO2) In the case of the transition metals a coordination number of 2 occurs with small ligands for electronic reasons, e.g with a d10 electron configuration. Examples for these complexes include the Ag(I), Cu(I), Au(I) and Hg(II) complexes Ag[NH3]2+ (the silver diammine complex that is formed, when AgCl is dissolved in ammonia), [CuCl2]-, [AuClPR3] (phosphine gold(I) chloride complexes), and [Hg(CH3)2] (dimethylmercury)

- Bent Bent geometries can be a result of lone pairs in main group chemistry.As a result of the steric demand of nonbonding lone pair electrons, these need room but are not visible in the structure. For example in the case of water with 4 electron pairs, two of which are lone pairs, a bent molecular geometry is the result.

Coordination Number 3 The coordination number 3 is also relatively rare for transition metals. It occus in the case of d10 complexes and when bulky ligands are present. Most transition metal examples are trigonal planar, some with a slight tendancy for pyramidalization.

Trigonal planar Well known for main group species like CO32- etc., this geometry has the four atoms in a plane with the bond angles between the ligands at 120 degrees.

The following structures represent examples for trigonal planar geometries.Main group geometries with 3 bonding electron pairs are trigonal planar BF3 tert-butyl cation

Trigonal planar - D3h [Cu(CN)3]2Trigonal pyramid More common with main group ions. T-shaped The first example of a rare T-shaped molecule was found in 1977 however since then several further examples have been reported.

T-shaped The T-shaped geometry is only observed for hypervalent main group elements in compounds such as iodine trichloride, chlorine trifluoride etc.

[Cu(PNP)]SbF6 where PNP= (2,6-bis[(di-tert-butylphosphino)methyl]pyridine) Coordination Number 4 Two different geometries are possible. The tetrahedron is the more common while the square planar is found almost exclusively with metal ions having a d8 electronic configuration.

Tetrahedral Typically, oxoanions like permanganate (MnO4-) and other compounds with metaloxygen or metal nitrogen multiple bonds (e.g. OsO4) have tetrahedral geometries. Another class of compounds are the halo-anions of Ni(II), Co(II), Cu(II) and Fe(II)/Fe(III). Methane Cu(bipy)4+ FeCl4OsO2(NtBu)2

-Square Planar The square planar rearrangement is preferred for d8 electron complexes of the second and third row and sometimes 1st row, e.g. Au(III), Pt(II), Ir(I). Sometimes the square planar eometry can be distorted, as in the Pd complex shown on the right below, due to steric demand of the ligands.

Tetrahedral, (Td) The chemistry of molecules centred around a tetrahedral C atom is covered in organic courses. To be politically correct, please change all occurrences of C to Co. There are large numbers of tetrahedral Cobalt(II) complexes known. e.g CoCl2pyr2 Square Planar, (D4h) These are much less common than tetrahedral and are included only because some extremely important molecules exist with this shape. cisplatin cis-PtCl2(NH3)2. The cis- isomer is a powerful anti-cancer drug whereas the trans- is inactive. Coordination Number 5 For coordination number 5, there are 2 basic geometries, trigonal bipyramidal and square pyramidal, and distorted versions thereof. Main group compounds mostly prefer the trigonal bipyramidal geometry. It is difficult to predict for the transition metals which structure a compoundwill adopt. Since the two structure types are only slightly different in energy, in many cases, for the same molecule or ion, depending on the conditions (packing in the solid state or counterion), both geometries can be seen. The anion [Ni(CN)5]3- can be seen in the same crystal, adopting both geometries. This is due to the stereochemical nonrigidity of the structures.

Square pyramid, (C4v) Trigonal Bipyramid, (D3h) Trigonal Bipyramidal

Compounds like iron pentacarbonyl (Fe(CO)5) and PF5 adopt the trigonal bipyramidal geometries. If all the ligands are the same, the point group for trigonal bipyramical structures is D3h. In trigonal biyramidal structures, there are 2 positions for the ligands, 2 axial and 3 equatorial positions.

The structure of [Cr(en)3][Ni(CN)5] 1.5 H2O was reported in 1968 to be a remarkable example of a complex exhibiting both types of geometry in the same crystal. The reaction of cyanide ion with Ni2+ proceeds via several steps: Ni2+ + 2 CN Ni(CN)2 Ni(CN)2 + 2 CN [Ni(CN)4]2orange-red log(4) = 30.1 [Ni(CN)5]3deep red Oxovanadium salts (Vanadyl, VO2+) often show square pyramidal geometry, for example, VO(acac)2. Note that the Vanadium(IV) can be considered coordinatively unsaturated and addition of pyridine leads to the formation of an octahedral complex. + CN Coordination Number 6 [Ni(CN)4]2-

Hexagonal planar Unknown for first row transition metal ions, although the arrangement of six groups in a plane is found in some higher coordination number geometries. Trigonal prism

Most trigonal prismatic compounds have three bidentate ligands such as dithiolates or oxalates and few are known for first row transition metal ions. tris(cis-1,2-diphenylethene-1,2-dithiolato)rhenium

Trigonal Prismatic The trigonal prismatic structure is only rarely adopted. The few examples known include hexamethyl complexes with d0 configuration, such as hexamethyltungsten and [Zr(CH3)6]2-.

Octahedral, (Oh) The most common geometry found for first row transition metal ions, including all aqua ions. In some cases distortions are observed and these can sometimes be explained in terms of the Jahn-Teller Theorem. [CoCO3(NH3)5]+

Octahedral In case of 6 monoatomic ligands, an undistorted octahedron also has the high octahedral symmetry and belongs to the point group Oh.

Coordination Number 7

Three geometries are possible: Not very common for 1st row complexes and the energy difference between the structures seems small and distortions occur so that prediction of the closest "idealised" shape is generally difficult.

Capped octahedron, (C3v) e.g K3[NbOF6]

Capped Octahedral In case of 6 monoatomic ligands, an undistorted octahedron also has the high octahedral symmetry and belongs to the point group Oh.

Capped trigonal prism, (C2v) e.g [V(III)(Hedta)(H2O)]H2O

Capped Trigonal Prismatic The trigonal prismatic structure is only rarely adopted. The few examples known include hexamethyl complexes with d0 configuration, such as hexamethyltungsten and [Zr(CH3)6]2-. Like all capped structures, in this case the base of the structure is a known polyhedron. The additional ligand is added on top of a face of the trigonal prism. Slight distortions can occur to accomodate the additional ligand, which is shown in blue in the following picture.

Pentagonal Bipyramid, (D5h) e.g bis-(tert-butylacac)2(DMSO)di-oxoUranium

Pentagonal Bipyramidal There are 2 different ligand positions in this structure, 2 axial and 5 equatorial positions. This structure type is adopted in many cases, where there is a macrocyclic pentadentate ligand, that occupies the equatorial positions.

Coordination Number 8

For eight-coordination, there are 3 main structure types, two of which are preferred for molecules. The Cubic structure, the Square Antiprism andthe Dodecahedron.

Dodecahedron, (D2d) e.g [Zr(acac)2(NO3)2], [Zr(C2O4)4]4

There are several ways to construct a dodecahedron. One method empoys two trapezoids that are perpendicular to each other in space. The other possibility is to imagine the polyhedron composed of two ....

Cube, (Oh)

Cubic The cubic coordination is is observed for ionic compounds because of steric reasons, it is not realized for molecular structures. A prime example is the structure of CsCl.

Square antiprism, (D4d) e.g U(acac)4

The square antiprism can be derived from a cube by trurning one of the faces with respect to the opposite face.

Hexagonal bipyramid, (D6h) e.g UO2(OAc)3 Coordination Number 9 Three-face centred trigonal prism, (D3h) e.g Hydrated salts of the lanthanide elements eg Eu(H2O)9]3+

Tricapped trigonal prismatic This structure type is very common for the nine-coordinate geometry. One historically important example is the ReH92- ion

Coordination Number 10 Bicapped square antiprism, (D4d) e.g Tetrakis(nitrato-O,O')-bis(triphenylphosphine oxide) cerium(IV) Coordination Number 11 All-faced capped trigonal prism, (D3h) This is not a common stereochemistry. In aqua-(12-crown-4)-tris(nitrato-O,O')-cerium(III) (12-crown-4) solvate and (15-crown-5)-tris(nitratoO,O')-cerium(III) the Cerium ion is 11 coordinate. Coordination Number 12 cuboctahedron, (Oh) Ceric ammonium nitrate -(NH4)2Ce(NO3)6