page_title: Coordination number
section_title: Complications
hierarchical_section_title: Coordination number / Case studies / Complications
caption_attribution_description: English: crystal structure of en:nickel arsenide Deutsch: Kristallstruktur von de:Nickelarsenid
context_page_description: 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. 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.
context_section_description: In some compounds the metal-ligand bonds may not all be at the same distance. For example in PbCl₂, the coordination number of Pb²⁺ could be said to be seven or nine, depending on which chlorides are assigned as ligands. Seven chloride ligands have Pb-Cl distances of 280–309 pm. Two chloride ligands are more distant, with a Pb-Cl distances of 370 pm.
  In some cases a different definition of coordination number is used that includes atoms at a greater distance than the nearest neighbours. The very broad definition adopted by the International Union of Crystallography, IUCR, states that the coordination number of an atom in a crystalline solid depends on the chemical bonding model and the way in which the coordination number is calculated.
  Some metals have irregular structures. For example, zinc has a distorted hexagonal close packed structure. Regular hexagonal close packing of spheres would predict that each atom has 12 nearest neighbours and a triangular orthobicupola (also called an anticuboctahedron or twinned cuboctahedron) coordination polyhedron. In zinc there are only 6 nearest neighbours at 266 pm in the same close packed plane with six other, next-nearest neighbours, equidistant, three in each of the close packed planes above and below at 291 pm. It is considered to be reasonable to describe the coordination number as 12 rather than 6. Similar considerations can be applied to the regular body centred cube structure where in addition to the 8 nearest neighbors there 6 more, approximately 15% more distant, and in this case the coordination number is often considered to be 14.
  
  Many chemical compounds have distorted structures. Nickel arsenide, NiAs has a structure where nickel and arsenic atoms are 6-coordinate. Unlike sodium chloride where the chloride ions are cubic close packed, the arsenic anions are hexagonal close packed. The nickel ions are 6-coordinate with a distorted octahedral coordination polyhedron where columns of octahedra share opposite faces. The arsenic ions are not octahedrally coordinated but have a trigonal prismatic coordination polyhedron. A consequence of this arrangement is that the nickel atoms are rather close to each other. Other compounds that share this structure, or a closely related one are some transition metal sulfides such as FeS and CoS, as well as some intermetallics. In cobalt(II) telluride, CoTe, the six tellurium and two cobalt atoms are all equidistant from the central Co atom.
  Two other examples of commonly-encountered chemicals are Fe₂O₃ and TiO₂. Fe₂O₃ has a crystal structure that can be described as having a near close packed array of oxygen atoms with iron atoms filling two thirds of the octahedral holes. However each iron atom has 3 nearest neighbors and 3 others a little further away. The structure is quite complex, the oxygen atoms are coordinated to four iron atoms and the iron atoms in turn share vertices, edges and faces of the distorted octahedra. TiO₂ has the rutile structure. The titanium atoms 6-coordinate, 2 atoms at 198.3 pm and 4 at 194.6 pm, in a slightly distorted octahedron. The octahedra around the titanium atoms share edges and vertices to form a 3-D network. The oxide ions are 3-coordinate in a trigonal planar configuration.
caption: NiAs structure
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