Английская Википедия:Coordination geometry

Материал из Онлайн справочника
Перейти к навигацииПерейти к поиску

Шаблон:Short description Шаблон:Main 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.[1]

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|Шаблон:Chem2]] as high as 20 in [[Organothorium chemistry|Шаблон:Chem2]].[2]

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.[1] 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).

Coordination number Geometry Examples of discrete (finite) complex Examples in crystals (infinite solids)
2 linear Файл:Linear-3D-balls.png Шаблон:Chem2 in Шаблон:Chem2 [3] Ag in silver cyanide,
Au in AuI [2]
3 trigonal planar Файл:Trigonal-3D-balls.png Шаблон:Chem2[2] O in [[titanium dioxide|Шаблон:Chem2]] rutile structure[3]
4 tetrahedral Файл:Tetrahedral-3D-balls.png Шаблон:Chem2[2] Zn and S in zinc sulfide, Si in silicon dioxide[3]
4 square planar Файл:Square-planar-3D-balls.png Шаблон:Chem2[2] CuO[3]
5 trigonal bipyramidal Файл:Trigonal-bipyramidal-3D-balls.png Шаблон:Chem2[3]
5 square pyramidal Файл:Square-pyramidal-3D-balls.png Шаблон:Chem2 in Шаблон:Chem2[2]
6 octahedral Файл:Octahedral-3D-balls.png Шаблон:Chem2[2] Na and Cl in NaCl[3]
6 trigonal prismatic Файл:Prismatic TrigonalP.png [[Hexamethyltungsten|Шаблон:Chem2]][4] As in NiAs, Mo in [[molybdenum disulfide|Шаблон:Chem2]][3]
7 pentagonal bipyramidal Файл:Pentagonal-bipyramidal-3D-balls.png Шаблон:Chem2 in Шаблон:Chem2[3] Pa in [[Protactinium(V) chloride|Шаблон:Chem2]]
7 capped octahedral Файл:Face-capped octahedron.png Шаблон:Chem2[5] La in [[lanthanum(III) oxide|A-Шаблон:Chem2]]
7 capped trigonal prismatic Файл:MonocappTrigPrism.CapRightps.png Шаблон:Chem2 in Шаблон:Chem2[3]
8 square antiprismatic Файл:Square-antiprismatic-3D-balls.png Шаблон:Chem2 in Шаблон:Chem2[3]
Шаблон:Chem2 aqua complex[6]
Thorium(IV) iodide[3]
8 dodecahedral
(note: whilst this is the term generally
used, the correct term is "bisdisphenoid"[3]
or "snub disphenoid" as this polyhedron is a deltahedron)
Файл:Snub disphenoid.png Шаблон:Chem2 in Шаблон:Chem2[3] Zr in Шаблон:Chem2[3]
8 bicapped trigonal prismatic Файл:Square face bicapped trigonal prism.png Шаблон:Chem2[7] Шаблон:Chem2[3]
8 cubic Caesium chloride, calcium fluoride
8 hexagonal bipyramidal Файл:Hexagonale bipiramide.png N in [[lithium nitride|Шаблон:Chem2]][3]
8 octahedral, trans-bicapped Ni in nickel arsenide, NiAs; 6 As neighbours + 2 Ni capping[8]
8 trigonal prismatic, triangular face bicapped Ca in Шаблон:Chem2[3]
9 tricapped trigonal prismatic Файл:AX9E0-3D-balls.png Шаблон:Chem2 in potassium nonahydridorhenate[2]
Шаблон:Chem2 aqua complex[6]
Шаблон:Chem2, Th in Шаблон:Chem2[3]
9 capped square antiprismatic Файл:Monocapped square antiprism.png Шаблон:Chem2[2]Шаблон:Cln La in Шаблон:Chem2[3]
10 bicapped square antiprismatic Шаблон:Chem2[2]
11 Th in Шаблон:Chem2 (Шаблон:Chem2 is bidentate)[2]
12 icosahedron Файл:Icosahedron.png Th in Шаблон:Chem2 ion in Шаблон:Chem2[3]
12 cuboctahedron Файл:Cuboctahedron.png Шаблон:Chem2 atoms in fcc metals e.g. Ca[3]
12 anticuboctahedron (triangular orthobicupola) Файл:Triangular orthobicupola.png atoms in hcp metals e.g. Sc[3]
12 bicapped hexagonal antiprismatic Шаблон:Chem2[2]

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.[9]
IUCr have proposed a symbol which is shown as a superscript in square brackets in the chemical formula. For example, Шаблон:Chem2 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.[1]
The IUPAC symbol is applicable to complexes and molecules whereas the IUCr proposal applies to crystalline solids.

See also

References

Шаблон:Reflist

  1. 1,0 1,1 1,2 Шаблон:Cite journal
  2. 2,00 2,01 2,02 2,03 2,04 2,05 2,06 2,07 2,08 2,09 2,10 2,11 Шаблон:Greenwood&Earnshaw
  3. 3,00 3,01 3,02 3,03 3,04 3,05 3,06 3,07 3,08 3,09 3,10 3,11 3,12 3,13 3,14 3,15 3,16 3,17 3,18 3,19 3,20 3,21 Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications Шаблон:ISBN
  4. Шаблон:Housecroft2nd
  5. Шаблон:Cite journal
  6. 6,0 6,1 Шаблон:Cite journal
  7. Шаблон:Cite journal
  8. David G. Pettifor, Bonding and Structure of Molecules and Solids, 1995, Oxford University Press,Шаблон:ISBN
  9. NOMENCLATURE OF INORGANIC CHEMISTRY IUPAC Recommendations 2005 ed. N. G. Connelly et al. RSC Publishing http://www.chem.qmul.ac.uk/iupac/bioinorg/