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The Structures of Complexes

The Structures of Complexes

The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar (see the figure below). For transition metal complexes, the coordination number determines the geometry around the central metal ion. The table below compares coordination numbers to the molecular geometry:

This figure contains three diagrams in black and white. The first is labeled, “Pentagonal Bipyramid.” It has 10 isosceles triangle faces, five at the top, joined at a vertex, making a point projecting upward at the top of the figure, and five below, joined at a vertex, making a point projecting downward, at the base of the figure. The second is labeled, “Square Antiprism.” It has flat upper and lower square surfaces and sides made up of 8 equilateral triangles. The sides alternate in orientation between pointing up and pointing down. The third diagram is labeled, “Dodecahedron.” It has twelve isosceles triangle faces.

These are geometries of some complexes with coordination numbers of seven and eight.

Coordination Numbers and Molecular Geometry
Coordination NumberMolecular GeometryExample
2linear[Ag(NH3)2]+
3trigonal planar[Cu(CN)3]2−
4tetrahedral(d0 or d10), low oxidation states for M[Ni(CO)4]
4square planar (d8)[NiCl4]2−
5trigonal bipyramidal[CoCl5]2−
5square pyramidal[VO(CN)4]2−
6octahedral[CoCl6]3−
7pentagonal bipyramid[ZrF7]3−
8square antiprism[ReF8]2−
8dodecahedron[Mo(CN)8]4−
9 and abovemore complicated structures[ReH9]2−

Unlike main group atoms in which both the bonding and nonbonding electrons determine the molecular shape, the nonbonding d-electrons do not change the arrangement of the ligands. Octahedral complexes have a coordination number of six, and the six donor atoms are arranged at the corners of an octahedron around the central metal ion. Examples are shown in the figure below. The chloride and nitrate anions in [Co(H2O)6]Cl2 and [Cr(en)3](NO3)3, and the potassium cations in K2[PtCl6], are outside the brackets and are not bonded to the metal ion.

Three structures are shown. In a, a structure is shown with a central C o atom. From the C o atom, line segments indicate bonds to H subscript 2 O molecules above and below the structure. Above and to both the right and left, dashed wedges indicate bonds to two H subscript 2 O molecules. Similarly, solid wedges below to both the right and left indicate bonds to two more H subscript 2 O molecules. Each bond in this structure is directed toward the O atom in each H subscript 2 O structure. This structure is enclosed in brackets. Outside the brackets to the right is the superscript 2 plus. Following this to the right appears 2 C l superscript negative sign. In b, a central C r atom has six N H subscript 2 groups attached with single bonds. These bonds are indicated with line segments extending above and below, dashed wedges extending up and to the left and right, and solid wedges extending below and to the left and right. The bonds to these groups are all directed toward the N atoms. The N H subscript 2 groups are each connected to C atoms of C H subscript 2 groups extending outward from the central C o atom. These C H subscript 2 groups are connected in pairs with bonds indicated by short line segments. This entire structure is enclosed in brackets. Outside the brackets to the right is the superscript 3 plus. Following to the right is 3 N O subscript 3 superscript negative sign. In c, 2 K superscript plus is followed by a structure in brackets. Inside the brackets is a central P t atom. From the P t atom, line segments indicate bonds to C l atoms above and below the structure. Above and to both the right and left, dashed wedges indicate bonds to C l atoms. Similarly, solid wedges below to both the right and left indicate bonds to two more C l atoms. This structure is enclosed in brackets. Outside the brackets to the right is the superscript 2 negative sign.

Many transition metal complexes adopt octahedral geometries, with six donor atoms forming bond angles of 90° about the central atom with adjacent ligands. Note that only ligands within the coordination sphere affect the geometry around the metal center.

For transition metals with a coordination number of four, two different geometries are possible: tetrahedral or square planar. Unlike main group elements, where these geometries can be predicted from VSEPR theory, a more detailed discussion of transition metal orbitals (discussed in the section on Crystal Field Theory) is required to predict which complexes will be tetrahedral and which will be square planar.

In tetrahedral complexes such as [Zn(CN)4]2− (see the figure below), each of the ligand pairs forms an angle of 109.5°. In square planar complexes, such as [Pt(NH3)2Cl2], each ligand has two other ligands at 90° angles (called the cis positions) and one additional ligand at an 180° angle, in the trans position.

Two structures are shown. In a, inside of brackets, a central Z n atom is bonded to 4 C atoms in a tetrahedral spatial arrangement. Short line segments are used to represent a bond extending above and down and to the left of the Z n atom. A dashed wedge with the vertex at the Z n atom and wide end at the C atom is used to represent a bond down and to the right of the Z n atom. The final bond is indicated by a similar solid wedge again directed down and only slightly right of the center beneath the Z n atom. Four groups of three parallel short line segments are shown indicating triple bonds extending from each C atom opposite the bond with Z n to an associated N atom. Outside the brackets a superscript of 2 negative is shown. In b, at the center of this structure is a P t atom. From this atom, a single bond represented by a dashed wedge extends from a vertex at the P t atom up and to the right to the N atom of an N H subscript 3 group. Similarly, a single bond represented by a solid wedge extends from a vertex at the P t atom down and to the right to the N atom of an N H subscript 3 group. Another single bond represented by a dashed wedge extends from a vertex at the P t atom up and to the left to a C l atom. Similarly, a single bond represented by a solid wedge extends from a vertex at the P t atom down and to the left to a C l atom.

Transition metals with a coordination number of four can adopt a tetrahedral geometry (a) as in K2[Zn(CN)4] or a square planar geometry (b) as shown in [Pt(NH3)2Cl2].

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