Layered compounds structures

G. A. Wiegers, Misfit Layer Compounds Structures and Physical Properties, Prog. Solid State Chem., 24, 1-139 (1996). 

The crystal structure of many compounds is dominated by the effect of H bonds, and numerous examples will emerge in ensuing chapters. Ice (p. 624) is perhaps the classic example, but the layer lattice structure of B(OH)3 (p. 203) and the striking difference between the a- and 6-forms of oxalic and other dicarboxylic acids is notable (Fig. 3.9). The more subtle distortions that lead to ferroelectric phenomena in KH2PO4 and other crystals have already been noted (p. 57). Hydrogen bonds between fluorine atoms result in the formation of infinite zigzag chains in crystalline hydrogen fluoride... 

Crystal chemistry ofTa and Nb fluorides - Compounds with layered-type structures... 

A further decrease in the X Me ratio, to 4, leads to linkage of the octahedral units by sharing more than one ligand so as to achieve coordination saturation. Sharing of two vertexes (two comers of the each octahedron) leads to the formation of compounds with layered-type structures. 

Tributsch H (1982) Photoelectrochemical Energy Conversion Involving Transition Metal d-States and Intercalation of Layer Compounds. 49 127-175 Truter MR (1973) Structures of Organic Complexes with Alkali Metal Ions. 16 71-111 Tytko KH, Mehmke J, Kurad D (1999) Bond Length-Bond Valence Relationships, With Particular Reference to Polyoxometalate Chemistry. 93 1-64 Tytko KH (1999) A Bond Model for Polyoxometalate Ions Composed of M06 Octahedra (MOk Polyhedra with k > 4). 93 65-124... 

Li Q, Walter EC, van der Veer WE, Murray BJ, Newberg JT, Bohannan EW, Switzer JA, Hemminger JC, Penner RM (2005) Molybdenum disulfide nanowires and nanoribbons by electrochemical/chemical synthesis. J Phys Chem B 109 3169-3182 Tenne R, Homyonfer M, Feldman Y (1998) Nanoparticles of layered compounds with hollow cage structures (inorganic fuUerene-like structures). Chem Mater 10 3225-3238 Shibahara T (1993) Syntheses of sulphur-bridged molybdenum and tungsten coordination compounds. Coord Chem Rev 123 73-147... 

In the following the compounds will be described, depending on the degree of condensation of the metal and trimetaphosphimate ions. Up to now phosphimatometallates with isolated and chainlike (single and double chains) units as well as a layered compound have been described. These structural possibilities are shown in Fig. 4. 

Solv=MeOH, EtOH and PrOH), and l,4-bis(4-pyridyl-butadiyne) (bpb, n= 0.5, Solv=MeOH). Like the btr derivative, compressed [FeN6] pseudo-octahedral sites define the knots of the square- or rhombus-shaped windows, which constitute the layered grid structure of the three compounds. Stacking of these layers in the crystal defines their most important structural differences, which are determined by the ligand size and crystal packing efficiency. In principle, the 2D grids are organised in a fashion similar to that described for the [Fe(btr)2(NCX)2]-H20 system the parallel layers are alternated so that the iron atoms of one layer lie vertically above and below the centres of the squares formed by the iron atoms of the adjacent layers. 

Figure 4.31 Idealized structures of misfit-layer compounds (a) (LaS)i.20CrS2 (b) (SnS)i.i7 NbS2 (c) (Ca2CoO3)0.62(CoO2) and (d) (Bi0.87SrO2)2(CoO2)i.s2. The shaded polyhedra represent sheets of MX6 octahedra (a, c, d) or trigonal prisms (b).

Organic phosphonates represent another class of anchoring agents, which react with zirconium hydroxide to form pillared structures. These are also referred to as molecularly engineered layered structures (MELS). Layered compounds of organic phosphonates of zirconium with the formula of Zr(RP03)2 have been rec-... 

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