Coordination geometry#Table of coordination geometries

{{Short description|Term used in chemistry}}

{{main|Molecular geometry}}

The coordination geometry of an atom is the geometrical pattern defined by the atoms around the central atom. The term is commonly applied in the field of inorganic chemistry, where diverse structures are observed. The coordination geometry depends on the number, not the type, of ligands bonded to the metal centre as well as their locations. The number of atoms bonded is the coordination number.

The geometrical pattern can be described as a polyhedron where the vertices of the polyhedron are the centres of the coordinating atoms in the ligands.{{cite journal | title = Report of the International Union of Crystallography Commission on Crystallographic Nomenclature Subcommittee on the Nomenclature of Inorganic Structure Types | journal = Acta Crystallogr. A | volume = 46 | pages = 1–11 | year = 1990 | doi = 10.1107/S0108767389008834 | author1 = J. Lima-de-Faria | author2 = E. Hellner | author3 = F. Liebau | author4 = E. Makovicky | author5 = E. Parthé | doi-access = free }}

The coordination preference of a metal often varies with its oxidation state. The number of coordination bonds (coordination number) can vary from two in Potassium dicyanoargentate as high as 20 in Organothorium chemistry.{{Greenwood&Earnshaw}}

One of the most common coordination geometries is octahedral, where six ligands are coordinated to the metal in a symmetrical distribution, leading to the formation of an octahedron if lines were drawn between the ligands. Other common coordination geometries are tetrahedral and square planar.

Crystal field theory may be used to explain the relative stabilities of transition metal compounds of different coordination geometry, as well as the presence or absence of paramagnetism, whereas VSEPR may be used for complexes of main group element to predict geometry.

Crystallography usage

In a crystal structure the coordination geometry of an atom is the geometrical pattern of coordinating atoms where the definition of coordinating atoms depends on the bonding model used. For example, in the rock salt ionic structure each sodium atom has six near neighbour chloride ions in an octahedral geometry and each chloride has similarly six near neighbour sodium ions in an octahedral geometry. In metals with the body centred cubic (bcc) structure each atom has eight nearest neighbours in a cubic geometry. In metals with the face centred cubic (fcc) structure each atom has twelve nearest neighbours in a cuboctahedral geometry.

Table of coordination geometries

A table of the coordination geometries encountered is shown below with examples of their occurrence in complexes found as discrete units in compounds and coordination spheres around atoms in crystals (where there is no discrete complex).

class="wikitable"

!style="text-align: center;"|Coordination number !! Geometry !! !! Examples of discrete (finite) complex !! Examples in crystals (infinite solids)

style="text-align: center;"| 2

|style="text-align: center;"|linear

100px{{chem2|[Ag(CN)2]−}} in {{chem2|K[Ag(CN)2]}} Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications {{ISBN|0-19-855370-6}}Ag in silver cyanide,
Au in AuI
style="text-align: center;"|3

|style="text-align: center;"|trigonal planar

100px{{chem2|[HgI3]−}}O in titanium dioxide rutile structure
style="text-align: center;"|4

|style="text-align: center;"|tetrahedral

100px{{chem2|[CoCl4](2−)}}Zn and S in zinc sulfide, Si in silicon dioxide
style="text-align: center;"|4

|style="text-align: center;"|square planar

100px{{chem2|[AgF4]−}}CuO
style="text-align: center;"|5

|style="text-align: center;"|trigonal bipyramidal

100px{{chem2|[SnCl5]−}}
style="text-align: center;"|5

|style="text-align: center;"|square pyramidal

100px{{chem2|[InCl5](2−)}} in {{chem2|[N(CH2CH3)4]2[InCl5]}}
style="text-align: center;"|6

|style="text-align: center;"|octahedral

100px{{chem2|[Fe(H2O)6](2+)}}Na and Cl in NaCl
style="text-align: center;"|6

|style="text-align: center;"|trigonal prismatic

100pxHexamethyltungsten{{Housecroft2nd|page=725}}As in NiAs, Mo in molybdenum disulfide
style="text-align: center;"|7

|style="text-align: center;"|pentagonal bipyramidal

100px{{chem2|[ZrF7](3−)}} in {{chem2|[NH4]3[ZrF7]}}Pa in Protactinium(V) chloride
style="text-align: center;"|7

|style="text-align: center;"|capped octahedral

100px{{chem2|[MoF7]−}}{{cite journal | title = "Non-VSEPR" Structures and Bonding in d(0) Systems | first = Martin | last = Kaupp | journal = Angew Chem Int Ed Engl | year = 2001 | volume = 40 | issue = 1 | pages = 3534–3565 | doi = 10.1002/1521-3773(20011001)40:19<3534::AID-ANIE3534>3.0.CO;2-# | pmid = 11592184 }}La in lanthanum(III) oxide
style="text-align: center;"|7

|style="text-align: center;"|capped trigonal prismatic

100px{{chem2|[TaF7](2−)}} in {{chem2|K2[TaF7]}}
style="text-align: center;"|8

|style="text-align: center;"|square antiprismatic

100px{{chem2|[TaF8](3−)}} in {{chem2|Na3[TaF8]}}
{{chem2|[Zr(H2O)8](4+)}} aqua complex{{cite journal|last1=Persson|first1=Ingmar|title=Hydrated metal ions in aqueous solution: How regular are their structures?|journal=Pure and Applied Chemistry|volume=82|issue=10|year=2010|pages=1901–1917|issn=0033-4545|doi=10.1351/PAC-CON-09-10-22|doi-access=free}}
Thorium(IV) iodide
style="text-align: center;"|8

|style="text-align: center;"|dodecahedral
(note: whilst this is the term generally
used, the correct term is "bisdisphenoid"
or "snub disphenoid" as this polyhedron is a deltahedron)

100px{{chem2|[Mo(CN)8](4−)}} in {{chem2|K4[Mo(CN)8]*2H2O}}Zr in {{chem2|K2[ZrF6]}}
style="text-align: center;"|8

|style="text-align: center;"|bicapped trigonal prismatic

100px{{chem2|[ZrF8](4−)}}{{cite journal | title = Eight-Coordination | author1 = Jeremy K. Burdett | author2 = Roald Hoffmann | author3 = Robert C. Fay | journal = Inorganic Chemistry | year = 1978 | volume = 17 | issue = 9 | pages = 2553–2568 | doi = 10.1021/ic50187a041 }}{{chem2|PuBr3}}
style="text-align: center;"|8

|style="text-align: center;"|cubic

Caesium chloride, calcium fluoride
style="text-align: center;"|8

|style="text-align: center;"|hexagonal bipyramidal

100pxN in lithium nitride
style="text-align: center;"|8

|style="text-align: center;"|octahedral, trans-bicapped

Ni in nickel arsenide, NiAs; 6 As neighbours + 2 Ni cappingDavid G. Pettifor, Bonding and Structure of Molecules and Solids, 1995, Oxford University Press,{{ISBN|0-19-851786-6}}
style="text-align: center;"|8

|style="text-align: center;"|trigonal prismatic, triangular face bicapped

Ca in {{chem2|CaFe2O4}}
style="text-align: center;"|9

|style="text-align: center;"|tricapped trigonal prismatic

100px{{chem2|[ReH9](2−)}} in potassium nonahydridorhenate
{{chem2|[Th(H2O)9](4+)}} aqua complex
{{chem2|SrCl2*6H2O}}, Th in {{chem2|Rb[Th3F13]}}
style="text-align: center;"|9

|style="text-align: center;"|capped square antiprismatic

100px{{chem2|[Th(tropolonate)4(H2O)]}}{{cln|reason=What on this Earth is "tropolonate"??? Clear this jargon for an average mortal human being!|date=July 2023}}La in {{chem2|LaTe2}}
style="text-align: center;"|10

|style="text-align: center;"|bicapped square antiprismatic

{{chem2|[Th(C2O4)4](2−)}}
style="text-align: center;"|11Th in {{chem2|[Th^{IV}(NO3)4(H2O)3]}} ({{chem2|NO3−}} is bidentate)
style="text-align: center;"|12

|style="text-align: center;"|icosahedron

100pxTh in {{chem2|[Th(NO3)6](2−)}} ion in {{chem2|Mg[Th(NO3)6]*8H2O}}
style="text-align: center;"|12

|style="text-align: center;"|cuboctahedron

100px{{chem2|Zr^{IV}(η^{3}\−[BH4]4)}}atoms in fcc metals e.g. Ca
style="text-align: center;"|12

|style="text-align: center;"|anticuboctahedron (triangular orthobicupola)

100pxatoms in hcp metals e.g. Sc
style="text-align: center;"|12

|style="text-align: center;"|bicapped hexagonal antiprismatic

{{chem2|U[BH4]4}}

Naming of inorganic compounds

IUPAC have introduced the polyhedral symbol as part of their IUPAC nomenclature of inorganic chemistry 2005 recommendations to describe the geometry around an atom in a compound.NOMENCLATURE OF INORGANIC CHEMISTRY IUPAC Recommendations 2005 ed. N. G. Connelly et al. RSC Publishing http://www.chem.qmul.ac.uk/iupac/bioinorg/

IUCr have proposed a symbol which is shown as a superscript in square brackets in the chemical formula. For example, {{chem2|CaF2}} would be Ca[8cb]F2[4t], where [8cb] means cubic coordination and [4t] means tetrahedral. The equivalent symbols in IUPAC are CU−8 and T−4 respectively.

The IUPAC symbol is applicable to complexes and molecules whereas the IUCr proposal applies to crystalline solids.

See also

References