X-ray crystals

The formation of such materials may be monitored by several techniques. One of the most useful methods is and C-nmr spectroscopy where stable complexes in solution may give rise to characteristic shifts of signals relative to the uncomplexed species (43). Solution nmr spectroscopy has also been used to detect the presence of soHd inclusion compound (after dissolution) and to determine composition (host guest ratio) of the material. Infrared spectroscopy (126) and combustion analysis are further methods to study inclusion formation. For general screening purposes of soHd inclusion stmctures, the x-ray powder diffraction method is suitable (123). However, if detailed stmctures are requited, the single crystal x-ray diffraction method (127) has to be used. 

The stmcture of Pmssian Blue and its analogues consists of a three-dimensional polymeric network of Fe —CN—Fe linkages. Single-crystal x-ray and neutron diffraction studies of insoluble Pmssian Blue estabUsh that the stmcture is based on a rock salt-like face-centered cubic (fee) arrangement with Fe centers occupying one type of site and [Fe(CN)3] units randomly occupying three-quarters of the complementary sites (5). The cyanides bridge the two types of sites. The vacant [Fe(CN)3] sites are occupied by some of the water molecules. Other waters are zeoHtic, ie, interstitial, and occupy the centers of octants of the unit cell. The stmcture contains three different iron coordination environments, Fe C, Fe N, and Fe N4(H20), in a 3 1 3 ratio. 

X-Ray Diffraction. Because of the rapid advancement of computer technology (qv), this technique has become almost routine and the stmctures of moderately complex molecules can be estabUshed sometimes in as Htde as 24 hours. An example illustrating the method is offered by Reference 24. The reaction of the acrylate (20) with phenyldiazo derivatives results in the formation of pyrazoline (21). The stereochemistry of the substituents and the conformation of the ring can only be estabUshed by single crystal x-ray diffraction. 

These hydrated salts contain bidentate carbonate ligands and no water molecules are bound directly to the central metal atom. The only single-crystal x-ray diffraction studies available are those for salts of (4) (52—54) and the mineral tuliokite [128706 2-3], Na2BaTh(C03)2 -6H20], which contains the unusual Th(C02) 2 anion (5) (55). 

The trimetaUic uranyl cluster (U02)3(C03) 3 has been the subject of a good deal of study, including nmr spectroscopy (179—182) solution x-ray diffraction (182), potentiometric titration (177,183,184), single crystal x-ray diffraction (180), and exafs spectroscopy in both the soHd and solution states (180). The data in this area have consistendy led to the proposal and verification of a trimeric (U02)3(C03) 3 cluster (181,182,185). 

Fig. 12. Siemens SMART Single Crystal X-ray Diffractometer System.

A single-crystal x-ray stmcture determination has shown that the borate ion in the pentahydrate and in borax are identical (77). 

A single-crystal x-ray diffraction study has shown that the borate anion in anhydrous borax is polymeric in nature and is formed via oxygen bridging of triborate and pentaborate groups (83). The chemistry of anhydrous borax has been reviewed (73,84). 

A single-crystal x-ray diffraction study gives a stmctural formula of Na2 [B5 0g (0H)4]-3H2 0 and contains the pentaborate ion analogous to that found in the corresponding potassium compound (86). 

Siagle-crystal x-ray studies have shown that the borate ion ia the potassium compound is identical to that found ia borax (4) and has the stmctural formula K2[B405(0H)J -2H20 (122). 

Kennard, O., Hunter, W.N. Oligonucleotide structure a decade of results from single crystal x-ray diffraction studies. Q. Rev. Biophys. 22 327-379, 1989. 

Compounds in which conformational, rather than configurational, equilibria are influenced by the anomeric effect are depicted in entries 4—6. Single-crystal X-ray dilfiaction studies have unambiguously established that all the chlorine atoms of trans, cis, ira j-2,3,5,6-tetrachloro-l,4-dioxane occupy axial sites in the crystal. Each chlorine in die molecule is bonded to an anomeric carbon and is subject to the anomeric effect. Equally striking is the observation that all the substituents of the tri-0-acetyl-/ -D-xylopyranosyl chloride shown in entry 5 are in the axial orientation in solution. Here, no special crystal packing forces can be invoked to rationalize the preferred conformation. The anomeric effect of a single chlorine is sufficient to drive the equilibrium in favor of the conformation that puts the three acetoxy groups in axial positions. 

In addition to the above oxides M2O, M2O2, M4O6, MO2 and MO3 in which the alkali metal has the constant oxidation state 4-1, rubidium and caesium also form suboxides in which the formal oxidation state of the metal is considerably lower. Some of these intriguing compounds have been known since the turn of the century but only recently have their structures been elucidated by single crystal X-ray analysis. Partial oxidation of Rb at low temperatures gives RbeO which decomposes above —7.3°C to give copper-coloured metallic crystals of Rb902 ... 

The unexpectedly complex product was isolated as an almost colourless air-stable powder, and a single-crystal X-ray analysis showed that it had the molecular adamantane-like structure (5). This is very similar to the structure of the iso-electronic compound P4O10 (p. 504). 

The translucent, cream-coloured benzene solvate was characterized by single-crystal X-ray analysis and by Pnrnr spectroscopy. The first free phospha-alkyne stable to polymerization... 

M. J. Nolte, E. Singleton and M. Laing, J. Am. Chem. Soc. 97, 6396-400 (1975). An important paper showing how errors can arise even in careful single crystal X-ray studies, leading to incorrect inferences. 

Table 16-3. Single-crystal X-ray diffraction data for OPVs. 

In some sulfur extrusions from 2,7-di-/ Tt-butylthiepins a byproduct containing two sulfur atoms is obtained, along with the aromatic compound. The byproduct has been characterized as a thienothiophene by single crystal X-ray analysis.92... 

Addition of lithiated Ar-(4-methylphenylsulfonyl)-S-phenyl-S -(2-propenyl)sulfoximine to acyclic enones gives exclusively 1,4-a-adducts in high diastereomeric purity. The configuration of the adduct (R2 = R3 = C6H5) has been determined by a single crystal X-ray structure determination27. 

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