Alkaline earth metals coordination numbers

Bismuthides. Many intermetaUic compounds of bismuth with alkafl metals and alkaline earth metals have the expected formulas M Bi and M Bi, respectively. These compounds ate not saltlike but have high coordination numbers, interatomic distances similar to those found in metals, and metallic electrical conductivities. They dissolve to some extent in molten salts (eg, NaCl—Nal) to form solutions that have been interpreted from cryoscopic data as containing some Bi . Both the alkafl and alkaline earth metals form another series of alloylike bismuth compounds that become superconducting at low temperatures (Table 1). The MBi compounds are particularly noteworthy as having extremely short bond distances between the alkafl metal atoms. 

The stereochemistry of Mg and the heavier alkaline earth metals is more flexible than that of Be and, in addition to occasional compounds which feature low coordination numbers (2, 3 and 4), there are many examples of 6, 8 and 12 coordination, some with 7, 9 or 10 coordination, and even some with coordination numbers as high as 22 or 24, as in SrCdn, BaCdn and (Ca, Sr or Ba)Zni3. " Strontium is 5-coordinate on the hemisolvate [Sr(OC6H2Bu3)2(thf)3]. jthf which features a distorted trigonal bipyramidal structure with the two aryloxides in equatorial positions. ... 

The simplest of structures is the rock salt structure, depicted in Figure 2.2a. Magnesium oxide is considered to be the simplest oxide for a number of reasons. It is an ionic oxide with a 6 6 octahedral coordination and it has a very simple structure — the cubic NaCl structure. The structure is generally described as a cubic close packing (ABC-type packing) of oxygen atoms in the (111) direction forming octahedral cavities. This structure is exhibited by other alkaline earth metal oxides such as BaO, CaO, and monoxides of 3d transition metals as well as lanthanides and actinides such as TiO, NiO, EuO, and NpO. 

True metals alkali, alkaline earth metals, Al, Cu, Ag, Au, etc., having a high specific electrical conductivity (OhnG cm l) k = 105—106 and crystal structures of high symmetry and coordination numbers (CN = 8-12). 

These considerations go far to explain the selectivity behavior of a series of macroheterobicyclic ligands (Fig. 9). Table 4 shows that an increase in the number of coordination sites from 6 to 8 or 9 leads to an increased preference for large cations. Ligand VI, with 11 coordination sites is no longer suited for the complexation of even the largest alkali and alkaline earth metal cations. Furthermore, it is clear that a relatively large coordination number (5 6) is required to produce selectivity for divalent ions. 

This chapter discusses the coordination chemistry of selected main group and transition metal complexes with dipicolinic acid, its analogues, and derivatives as ligands. Selected elements will be presented in terms of increasing atomic number. Out of all of the alkali metals, there has been a report of the crystal structure of sodium coordinated to dipicolinic acid. Calcium, magnesium, and strontium, three alkaline earth metals, are popular metal centers, which have been reported in the literature to be coordinated to dipicolinic acid or its analogues. ... 

These results clearly indicate that the chelate ligation is driven primarily by the enthalpic factor and the entropy plays merely a trivial role in determining the complex stability. This is quite reasonable since the structures of these chelate complexes are strictly defined by the number and direction of the coordination sites of given heavy/transition metal ions, and therefore there is little room for the entropic term to adjust flexibly the complex structure and stability. On the contrary, alkali and alkaline earth metal ions also have the formal coordination numbers, but the actual number and direction of ligand coordination are highly flexible in the weak interaction-driven ligation by hard donors like glyme and crown ether. 

The alkaline earth metal cryptates have higher coordination numbers, with additional binding to solvent. 

PL is a useful technique to characterize the coordination not only of transition metal cations, as described above, but also of oxide anions. A typical coordination of oxide anions in the bulk lattices of oxides can be defined by the number of nearest neighbor cations for octahedrally coordinated alkaline earth oxides, this number is 6. Ions of lower... 

The calcium, strontium, barium, and lead 80) complexes of 160 and 161 have also been reported. In these two ligands the six donor atoms are essentially confined in a plane these complexes thus permit study of unusual coordination geometries in species of high coordination number. Attempts to form alkali metal complexes with 160 and 161 under the same conditions as employed for the alkaline earth metal complexes have failed. The successful syntheses of complexes of the latter type indicate that the higher charge to radius ratio is of consequence when spherically charged cations are employed. Such metal ions have no apparent coordinative discrimination as the template ion 87). 

If we consider the fluorides, for example, which form pure coordination lattices (p. 33), then those from the alkaline earth metals with the exception of magnesium and beryllium crystallize in the fluorite structure, in which the cation is surrounded by eight fluorine ions for CaF2 and CdF2, which have the same structure, r+/r is 0.71 and 0.69 respectively just at the limit V 3— 1 — 0.73. The fluorides of other divalent ions, such as Mn, Fe, Co and Ni and also Mg, crystallize in a structure with coordination number six (rutile type). It is only for BeF2 that the ratio r+/r = 0.23 lies below the limit of this coordination number and it has a structure similar to that of cristobalite (Si02) with four neighbours (see also p. 66). 

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