ISSN:
0009-2940
Keywords:
Ba14InP11
;
Zintl phase
;
Tetraphosphidoindate(III) anions
;
Asymmetric [P3]7- polyanions
;
Interpenetrating hierarchical frameworks
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Ba14InP11 was prepared from the elements in a sealed stainless steel ampoule at 1345 K. The compound is black, brittle and very sensitive to air and moisture. Ba14InP11 crystallises in the tetragonal Ca14AlSb11 type (space group I41/acd, No. 142; a = 17.097 (2) Å, c, = 8, Pearson code tI208). The structure contains isolated P3-, linear [P3]7- and tetrahedral [InP4]9- anions. The X-ray structure analysis and the vibrational spectra show that the [P3]7- polyanion is strongly asymmetric with d(P-P) = 2.28 Å and 4.10 Å, corresponding to a [P2]4- dumbbell weakly coupled to a single p3- anion. The tetraphosphidoindate(III) anion [InP4]9- is slightly compressed along the 4 axis, with bond lenght d(In-P) = 2.71 Å. It is shown that the structure is hierarchically related to that of Cu2O, with two interpenetrating frameworks, in which the O and Cu atoms are replaced by condensed [InP4/2] tetrahedron and [BaP4P2/2] octahedra, respectively. Both frameworks are meso configured, containing alternate R and S fragments. The other Ba cations envelop the P6 octahedra and P3 triads forming condensed cubes, tetragonal antiprisms and bicapped trigonal prisms. Therefore, the structure also forms a heterogeneous framework of centred PBa8/2tap tetragonal antiprisms and BaBa8/2cub cubes, consisting of two interpenetrating enantiomorphic nets (R and S) similar to those in the cubic phase RhBi4.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290907
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