Antiprisms

Ms " clusters have 12 framework bonding electrons as has [BsHs]- (p. 161) the anions are also isoelectronic with the well-known cation [Bis]. Similarly, the alloy NaSn. 2.23 reacts with cryptand in ethylenediamine to give dark-red crystals of [Na(ciypt)]4 [Sng] the anion is the first example of a C41, unicapped Archi-median antiprism (Fig. 10. lOc) and differs from the >3/, structure of the isoelectronic cation [Bis] + which, in the salt Bi+[Bi9] +[HfCl6]5 (p. 591), features a tricapped trigonal prism, as in [BgHg] " (p. 153). The emerald green species [Pb9] , which is stable in liquid NH3 solution, has not so far proved amenable to isolation via ciyptand-complexed cations. 

Chlorates and bromates feature the expected pyramidal ions X03 with angles close to the tetrahedral (106-107°). With iodates the interatomic angles at iodine are rather less (97-105°) and there are three short I-O distances (177-190 pm) and three somewhat longer distances (251-300 pm) leading to distorted perovskite structures (p. 963) with pseudo-sixfold coordination of iodine and piezoelectric properties (p. 58). In Sr(I03)2.H20 the coordination number of iodine rises to 7 and this increases still further to 8 (square antiprism) in Ce(I03)4 and Zr(I03)4. 

The most symmetrical structure possible is the cube Oh but, except in extended ionic lattices such as those of CsCl and CaF2, it appears that inter-ligand repulsions are nearly always (but see p. 1275) reduced by distorting the cube, the two most important resultant structures being the square antiprism D4h and the dodecahedron Did (Fig. 19.10). 

Figure 19.10 (a) Conversion of cube to square antiprism by rotation of one face through 45° (b) Conversion of cube into dodecahedron. 

Several carboxylates, both simple salts and complex anions, have been prepared often as a means of precipitating the An ion from solution or, as in the case of simple oxalates, in order to prepare the dioxides by thermal decomposition. In K4[Th(C204)4].4Fl20 the anion is known to have a 10-coordinate, bicapped square antipris-matic structure (Fig. 31.8b). -diketonates are precipitated from aqueous solutions of An and the ligand by addition of alkali, and nearly all are sublimable under vacuum. [An(acac)4], (An = Th, U, Np, Pu) are apparently dimorphic but both structures are based on an 8-coordinate, distorted square antiprism. 

Structural characteristics of compounds with X Me = 8 are collected in Table 17. Na3NbF8 and Na3TaF8 compounds that form similar crystal structure [77], The structure of Na3TaF8 was determined by Hoard et al. [136], by means of X-ray diffraction of a single crystal. Na3TaF8 is composed of sodium cations and isolated complex ions TaF83, in an Archimedean antiprism configuration, as shown in Fig. 23. 

The polyhedron NbF72 is more similar to a pentagonal bi-pyramid but is distorted due to a strong shift of F6 towards F3 (F6F3 and FiF distances are 2.39 and 3.08 A, respectively). This distortion renders the polyhedron structure closer to an Archimedes antiprism with a truncated comer, as shown in Fig. 31. 

Spot tests, 1, 552 Square antiprisms dodecahedra, cubes and, 1, 84 eight-coordinate compounds, 1,83 repulsion energy coefficients, 1, 33, 34 Square planar complexes, 1,191, 204 structure, 1, 37 Square pyramids five-coordinate compounds, 1,39 repulsion energy coefficients. 1,34 Squares... 

Magnetic measurements of PuFi, between 4.2 and 300 K are consistent at high temperatures with older measurements (10-12). The large temperature dependent diamagnetism observed earlier was not found. Up to 100 K the susceptibility is nearly temperature independent with a value of X ip 2940 x 10-6 emu. The Curie-Weiss behavior near room temperature indicates population of a higher first excited state. The structure of PuFi, is isomorphic with that of UFi, (13), where two different sets of actinide atoms are 8-fold coordinated by a distorted antiprism. 

The symmetry axis with maximum strength for each function of set I is 69° 1.35 from the fivefold axis of the pentagonal antiprism, corresponding to the ratio 0.38341 of half height to radius of the antiprism, with the corresponding values for set II of 41° 47.65 and 1.1186. 

The functions I accordingly correspond to an oblate antiprism and II to a prolate antiprism. There is a simple explanation for the difference in orientation of the principal axes. The theorem that the sum of the squares of the values of the functions for a complete set (a subshell) is constant requires that the shape parameters vary in a satisfactory way with change in orientation of the principal axes. For the prolate set (II) the maximum value in the plane orthogonal to the principal axis of the function lies in the basal plane of rhe antiprism, and thus serves to increase the electron... 

Figure 4. The oblate and prolate pentagonol antiprisms, the axes of which give the direction of the principal axes of the two sets of five equivalent d orbitals.

---