Polymorphic structures silver

Silver fulminate was recognized by Gay-Lussac16 to have the same composition as silver cyanate, thus providing the first example of isomerism. Two polymorphs of silver fulminate are known and their structures have been determined.17 Silver fulminate is regarded as a poor detonator due to its dangerous sensitivity this may depend on the presence or absence of the second form.17... 

Alpha silver iodide (a-Agl), a fast ion conductor, is one of the different polymorphic structures of Agl showing a cubic structure [51], where I occupies anionic positions, that is, the Cl- sites in the CsCl-type structure (see Figure 2.19). On the other hand, the low temperature phase, that is, p-Agl, exhibits a hexagonal wurtzite-type structure. 

The majority of unipolar ionic conductors identified to date are polymorphic compounds with several phase transitions, where the phases have different ionic conductivities owing to modifications in the substructure of the mobile ions [28], One of the first studied cationic conductors was a-Agl [21]. Silver iodide exhibits different polymorphic structures. Agl has a low-temperature phase, that is, [3-Agl, which crystallizes in the hexagonal wurtzite structure type, and a high-temperature cubic phase, a-Agl, which shows a cubic CsCl structure type [20,22] (see Section 2.4.5). 

When subjected to high temperatures and pressures, polymorphs have been prepared for some of the difluorides. These all have distorted variants of the fluorite structure, with cubic, or pseudocubic, tetragonal cells. Manganese difluoride has been most studied (28-30) and similar polymorphism reported for cobalt and zinc difluorides (30). Recently, palladium and silver difluorides have been shown to behave in a similar way forming cubic metastable phases (31). In all cases there is a decrease in volume for the structure change. 

Silver iodide, Agl, exists in several polymorphic forms. In the a-Agl crystal, the 1 ions adopt the bcp structure, and the Ag+ cations are distributed statistically among the 6(b), 12(d), and 24(h) sites of space group — Im3m, as listed in Table 10.3.1, and also partially populate the passageways between these positions. The cubic unit cell, with a — 504 pm, provides 42 possible positions for two Ag+ cations, and the Ag+ I- distances are listed below ... 

Tautomerization of porphyrins in crystals exhibits diverse patterns of behaviour. There are polymorphic crystal structures of tetraphenylporphyrin (TPP) [19] the tetragonal and the triclinic forms (Silvers and Tlilinsky, 1967 Codding and Tulinsky, 1972 Tblinsky, 1973). In the tetragonal form. X-ray... 

M SbOs. The salt NaSbOs may be prepared by heating NaSb(OH)g in air or by fusing Sb203 with sodium carbonate-there are similar silver and lithium salts. The sodium salt has the ilmenite structure the compound thought to be a polymorphic modification is actually Na2Sb205(OH)2 (see later). The structure ofLiSbOs is related to that of NaSb03 in the way described in Chapter 4. In both structures M and Sb each occupy one-third of the octahedral holes in a h.c.p. assembly of 0 atoms, but the choice of holes occupied is different in the two structures (p. 145). 

In recent years, W/O microemulsions have found numerous applications as microreactors for specific reactions (for comprehensive reviews, see Refs. 94 and 95). Thus, it has been shown that hydrophilic enzymes can be solubilized without loss of enzymatic activity and used to catalyze various chemical and photochemical reactions [96,97]. Other interesting applications involve the polymerization of solubilizates in microemulsions [98] and the preparation of micro-porous polymeric materials by polymerization of single-phase microemulsions [99]. Furthermore, microemulsions have been used as microreactors for the synthesis of nanosized particles for various applications [93,95] such as metal clusters (Pt, Pd, Rh, Au) for catalysis [100,101], semiconductor clusters [102-104] (ZnS, CdS, etc.), silver halides [105], calcium carbonates, and calcium fiuoride [106]. Recently it was shown [107,108] that it is possible to use W/O microemulsions for the control of polymorphism of water-soluble organic compounds. In most of these appUcations, one or more reactants are solubilized within a microemulsion and then a reaction is initiated. Depending on its molecular structure. 

Silver fulminate (SF) is a white crystalline material with heat of formatiOTi 179 kJ mol [15]. It crystallizes in the form of small rosettes or star-shaped clusters. Two polymorphic forms have been reported—orthorhombic and trigonal. The crystal shape depends on reaction conditions (temperature, concentration) during sUver fulminate preparation [94]. Recrystallization from ammonia leads to needles and multiple growths of leaf-like habits [92]. Long (4—5 mm) needle-shaped crystals were prepared by Singh and investigated by X-ray analysis. It was found that the crystal is orthorhombic [95]. The crystal structure of SF was later investigated in detail by Britton and Dunitz [96, 97] and their results were confirmed by Barrick et al. [98]. Ammonium acetate solution ( 20 %) is recommended as the solvent for... 

Silver salt of 5-nitrotetrazole is known to exist in six polymorphic forms which is the major disadvantage of this compound [4], whereas the mercuric salt does not exhibit polymorphism [54]. The very wide range of crystal structures of Hg(NT>2 has been reported [4]. The big drawback of mercury 5-nitrotetrazole is its incompatibility with aluminum [42]. 

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