Octahedral, distorted

When a copper(II) salt dissolves in water, the complex aquo-ion [Cu(H2p)6P is formed this has a distorted octahedral (tetragonal) structure, with four near water molecules in a square plane around the copper and two far water molecules, one above and one below this plane. Addition of excess ammonia replaces only the four planar water molecules, to give the deep blue complex [Cu(NH3)4(H20)2] (often written as [Cu(NHj)4] for simplicity). TTo obtain [Cu(NH3)6], water must be absent, and an anhydrous copper(II) salt must be treated with liquid ammonia. 

Addition of halide ions to aqueous copper(II) solutions can give a variety of halo-complexes for example [CuCl4] (yellow square-planar, but in crystals with large cations becomes a flattened tetrahedron) [CuClj] (red, units linked together in crystals to give tetrahedral or distorted octahedral coordination around each copper). 

Derivatives of Antimony Pentabromide and Pentaiodide. The existence of SbBr and Sbl is in doubt, although from time to time they are reported in the Hterature (35). The existence of a 1 1 adduct, SbBr 0(0244 )2, however, is generally accepted. In addition, the SbBr ion is known, and from x-ray studies has been found to have a slightly distorted octahedral stmcture (36). Indeed, there are quite a number of complex bromoantimony compounds with alkali metals and organic bases, some of wliich contain Sb(V). Thus the quinuclidinium salt (C24423N44)4Sb2Br2g is actually made up of... 

These hahdes generally display a coordination number of six, have a distorted octahedral geometry, are moisture sensitive, and are easily oxidized when exposed to humid air. 

Chromium (II) also forms sulfides and oxides. Chromium (II) oxide [12018-00-7], CrO, has two forms a black pyrophoric powder produced from the action of nitric acid on chromium amalgam, and a hexagonal brown-red crystal made from reduction of Cr202 by hydrogen ia molten sodium fluoride (32). Chromium (II) sulfide [12018-06-3], CrS, can be prepared upon heating equimolar quantities of pure Cr metal and pure S ia a small, evacuated, sealed quartz tube at 1000°C for at least 24 hours. The reaction is not quantitative (33). The sulfide has a coordination number of six and displays a distorted octahedral geometry (34). 

Fig. 16.13b (Se-Fax 180 pm, Se-Feq 167 pm, with axial and equatorial angles subtended at Se of 169.3° and 96.9°, respectively).However, these pseudo-tbp molecules are arranged in layers by weaker intermolecular interactions to neighbouring molecules so as to form an overall distorted octahedral environment with two further Se F at 266 pm (Fig. 16.13b) somewhat reminiscent of the structure found earlier for Tep4 (see Fig. 16.13c and below).

The other tetrahalides can all readily be made by direct reactions of the elements. Crystalline SeCU, TeCU and -SeBr4 are isotypic and the structural unit is a cubane-like tetramer of the same general type as [Me3Pt(/Z3-Cl)]4 (p. 1168). This is illustrated schematically for TeCU in Fig. 16.13d each Te is displaced outwards along a threefold axis and thus has a distorted octahedral environment. This can be visualized as resulting from repulsions due to the Te lone-pairs directed towards the cube centre and, in the limit, would result in the separation into... 

XeFs 49.5 Distorted octahedral (fluxional) Pentagonal bipyramidal or capped oct edral (1)... 

Xc02F2 CsXeOFj KXeOjF 30.8 C21, see-saw Distorted octahedral Square pyramidal (chain) Trigonal bipyramidal (1) Capped octahedral (1) Octahedral (1)... 

Octahedral Distorted octahedral [XeOs]"- XeFa(g), [XeOFj]- ... 

In fact the vast majority of 6-coordinate complexes are indeed octahedral or distorted octahedral. In addition to the twist distortion just considered distortions can be of two other types trigonal and tetragonal distortions which mean compression or elongation along a threefold and a fourfold axis of the octahedron respectively (Fig. 19.8). 

The most important members of this class are the osmium nitrido, and the osmyl complexes. The reddish-purple K2[OsNCl5] mentioned above is the result of reducing the osmiamate. The anion has a distorted octahedral structure with a formal triple bond Os=N (161pm) and a pronounced /ram-influence (pp. 1163-4), i.e. the Os-Cl distance trans to Os-N is much longer than the Os-Cl distances cis to Os-N (261 and 236 pm respectively). The anion [OsNCls] also shows a rram-effect in that the Cl opposite the N is more labile than the others, leading, for instance, to the formation of [Os NCl4] , which has a square-pyramidal structure with the N occupying the apical position. 

Other non-haem proteins, distinct from the above iron-sulfur proteins are involved in the roles of iron transport and storage. Iron is absorbed as Fe" in the human duodenum and passes into the blood as the Fe protein, transferrin, The Fe is in a distorted octahedral environment consisting of 1 x N, 3x0 and a chelating carbonate ion which... 

Figure 28.4 The anions of the chlorocomplex of stoichiometry, CsAuCl3, showing linearly coordinated Au and (4 + 2) tetragonally distorted, octahedral Au , i.e. Cs2[Au Cl2][Au CLt]-...

The most usual type of coordination in compounds of Hg with other donor atoms is a distorted octahedron with 2 bonds much shorter than the other 4. In the extreme, this results in linear 2-coordination in which case the bonds are largely covalent. Hg(CN)2 is actually composed of discrete linear molecules (C-bonded CN ), whereas crystalline Hg(SCN)2 is built up of distorted octahedral units, all SCN groups being bridging ... 

Similar halogeno complexes are produced in solution, and several salts of [HgXs]" have been isolated and characterized they display a variety of stereochemistries. In [HgCl3] the environment of the Hg is either distorted octahedral (with small cations such as NHj" "... 

The diammine [Hg(NH3)2Cl2], descriptively known as fusible white precipitate , can be isolated by maintaining a high concentration of NH4+, since reactions (2) and (3) are thereby inhibited, or better still by using non-polar solvents. It is made up of a cubic lattice of Cl ions with linear H3N-Hg-NH3 groups inserted so as to give the common, distorted octahedral coordination about Hg (Hg N = 203 pm, Hg-Cl = 287 pm) (Fig. 29.4a). 

The compound Ag(TaF6)2 crystallizes in triclinic syngony with cell parameters (A, grad.) as follows a = 9.061, b = 5.607, c = 5.207, a = 118.7, p = 91.61, y = 102.3. Ag(TaF6)2 is composed of two separate layers made up of octahedral ions AgF64 and distorted octahedral complexes NbFe that are linked through the planes. 

According to investigations performed by Pakhomov and Kaidalova [204], the crystal structure of NF NbC consists of infinite chains made up of distorted octahedral ions (NbOF4 ) linked by oxygen atoms. Ammonium cations, NH/, occupy the spaces between the chains, as shown in Fig. 30. The packing of the structural units in the NH4NbOF4 crystal can be described as a CsCl type structure in which CF ions are replaced by Nb02F4 complexes and Cs" ions are replaced by ammonium ions. 

The niobium atom has a slightly distorted octahedral coordination. Interatomic distances between the niobium atom and the two oxygen atoms in trans positions, O-Nb-O are 1.81 and 2.14 A. The niobium atom is shifted from the base plane of the octahedron by 0.23 A, and this shift, in adjacent chains, is in opposite directions. Pakhomov and Kaidalova [204] concluded that the shorter Nb-O bond (1.81 A) is an intermediate between a single and double bond. 

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