Copper nitrate structure

Mercuric halides, silver nitrate, and copper nitrates form stable complexes with bis-2.2 -thiazolylazo compounds (1591). for which the X-ray structure is not yet known. 

Covalent bonding of the nitrate group to a metal atom normally occurs only in the absence of water. Recent work on anhydrous metal nitrates has been concerned with both structure and chemical reactivity and it is now coming to be realized that these two aspects are closely interlinked. Generalizing, we may say that the stronger the covalent bond, the more reactive is the metal nitrate. Furthermore, extreme covalency leads to volatility (as with the volatile copper nitrate) and those nitrates which display volatility are also the most reactive chemically. 

Kitaura et al. obtained a new lamellar compound [Cu(dhbc)2(4,4 -bpy)] H20 from a diethyl ether solution of copper nitrate, 4,4 -bipyridine, and 2,5-dihydroxybenzoic acid (dhbc).[202] There are strong n-n interactions between the layers of the compound, and because of these interactions the compound behaves as a 3-D framework structure with channels containing guest water molecules that are removable reversibly. After dehydration, the host material exhibits adsorption properties, but its adsorption capacity for nitrogen is affected by the gas pressure. 

For the transition metal ions, Cr +, Fe " ", Fe +, Ni +, and Cu " have all been studied by NDIS methods, with the results attesting to the richness and uniqueness of structures these ions possess in aqueous solution. Of particular interest for these cations are results for Cu + which are strongly dependent on counterion and concentration. The exact details of the Cu + coordination remains controversial with claims for five-fold overall coordination in copper perchlorate solutions. For solutions of copper nitrate and copper perchlorate, there is no evidence for cation-anion contacts, however, in aqueous solutions of copper chloride at concentrations above three molal, there is strong evidence for copper-chloride compexation. 

Many ionic compounds can have water molecules incorporated into their solid structures. Such compounds are called hydrates. To emphasize the presence of discrete water molecules in the chemical structure, the formula of any hydrate shows the waters of hydration separated from the rest of the chemical formula by a dot. A coefficient before H2 O indicates the number of water molecules in the formula. Copper(II) sulfate pentahydrate is a good example. The formula of this beautiful deep blue solid is C11SO4 5 H2 O, indicating that five water molecules are associated with each CuSOq unit. Upon prolonged heating, CuSOq 5 H2 O loses its waters of hydration along with its color. Other examples of hydrates include aluminum nitrate nonahydrate, A1 (N03)3 9 H2 O,... 

The molecular structures of several [TpBut]ZnX derivatives have been determined by x-ray diffraction. For example, x-ray diffraction studies confirm that the acetate ligand in [TpBut]Zn(r)1-02CMe) is bound to zinc in a unidentate mode, similar to that proposed for [TpBut]Mg(7j1-02CMe), but in contrast to the bidentate coordination proposed for the copper analogue [TpBut]Cu(T)2-02CMe) (86,87). Such a change in coordination mode for copper and zinc derivatives is to be anticipated on the basis of structural studies on the nitrate derivatives [TpBut]M(N03) (M = Co, Ni, Cu, Zn), as described in Section V,B,2,e. The thioacetate [TpPh]-Zn V-SC(0)Me (81), and cyanoacetate [Tp lZnlr -C CCH N) (88) derivatives also exhibit unidentate coordination. 

The structural variations observed for [TpRR ]M(N03) (M = Co, Ni, Cu, Zn Cd) reveal that, for a given [Tp1 ] ligand, the preference for bidentate coordination increases across the series Zn < Co Cu, Ni, and Cd. Significantly, these structural preferences of the nitrate ligand correlate with the activity of the metal-substituted enzymes Zinc, the metal with the greatest tendency to exhibit unidentate coordination of the nitrate ligand, is the most active, while nickel, copper, and... 

The ability of cobalt(II), nickel(II), and copper(II) to exhibit a greater tendency than Zn(II) towards bidentate coordination is further illustrated by structural comparisons within a series of bridging carbonate complexes (188). For example, of the complexes [TpPr 2]M 2(/x-C03) (M = Mn, Fe, Co, Ni, Cu, Zn), only the zinc derivative does not exhibit bidentate coordination at both metal centers (151,153). Furthermore, the carbonate ligand in the complexes [TpPr 2]M 2(/x-C03) (M = Mn, Fe, Co, Ni, Cu) also exhibits varying degrees of asymmetry that closely parallel the series of nitrate complexes described earlier (Fig. 47 and Table IX). 

Table 3 Mean values and ranges (in parentheses) for the hydrogen-bonded contacts in the extended structures of the structurally characterised bis(AT-alkylamidino-0-alkylurea)copper(II) nitrates, tetrafluoroborates, halides and sulfates...

Mercuric-5-nitrotetrazole [Structure (2.13)] was prepared according to the methods reported by Gilligan et al. [14] and Redman and Spear [15]. Thus, 5-aminotetrazole was treated with sodium nitrite and copper sulfate to obtain Cu(NT)2HNT-4H20 (where NT nitrotetrazole). The copper salt was subsequently converted to the ethylene diamine complex MNT was then obtained by treating the complex with mercuric nitrate in HN03 medium. The precursors and final product were air dried. The synthesis of these compounds is carried out in a fume hood behind a protective polycarbonate shield in a stainless steel reaction vessel. 

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