Single-crystal structure

As the number of atoms in the asyimnetric unit increases, the solution of a structure by any of these phase-independent methods becomes more difficult, and by 1950 a PhD thesis could be based on a single crystal structure. At about that time, however, several groups observed that the fact that the electron density must be non-negative everywhere could be exploited to place restrictions on possible phases. The first use of this fact was by D Marker and J S Kasper [24], but their relations were special cases of more general relations introduced by J Karle and H Hauptman [25]. Denoting by A. the set of indices h., k., /., the Karle-Hauptman condition states that all matrices of the fonu... 

Small-Molecule Single-Crystal Structure Determination... 

In general, increasing the temperature within the stability range of a single crystal structure modification leads to a smooth change in all three parameters of vibration spectra frequency, half-width and intensity. The dependency of the frequency (wave number) on the temperature is usually related to variations in bond lengths and force constants [370] the half-width of the band represents parameters of the particles Brownian motion [371] and the intensity of the bands is related to characteristics of the chemical bonds [372]. 

Compound Preparation, properties Single crystals Structure Optical properties Phototropy Electric conductivity Magnetism... 

Laube and Hollenstein [21, 61] studied the single crystal structures of cyclohexanone derivatives complexed with a Lewis acid and found pyramidalization of the carbonyl carbon (4, Fig. 4), in agreement with the observed selectivity [61]. 

Correlation of the single-crystal structure results with the powder diffraction pattern, establishing x-ray powder diffraction as a convenient, powerful means of isomer identification and... 

LiZnGe single-crystal structure was refined using 253 observed reflections to Rl = 1.86% from Xcalibur CCD X-ray... 

Both dialkynylated cymantrenes 16 and 17 have the same symmetry and similar NMR spectra, so that the ultimate structure elucidation had to rest upon X-ray crystallography. It was reasoned that the dialkynylcymantrene with the smaller /(H,H) coupling of the cyclopentadienyl protons should be 17, an interpretation reinforced [23 a] by the result of the single-crystal structure. 

Stadler R, Jusys Z, Baltmschat H. 2002. Hydrogen evolution during the oxidation of formaldehyde on Au The influence of single crystal structure and Tl-upd. Electrochim Acta 47 4485-4500. 

An interesting Mossbauer study has been reported on the dinuclear SCO complex [Fe2 (PMAT)2](BF4)4-DMF (PMAT 4-amino-3,5-bis [(2-pyridylmethyl) amino]methyl -4H-1,2,4-triazole), where thermal ST occurs from [HS-HS] to the stable endproduct [HS-LS] [32]. The molecular structure and magnetic behavior of this complex was reported earlier by Brooker et al. [33, 34] (Fig. 8.15). At ca. 225 K, the complex undergoes a sharp half ST from the HS state, T2, to a state containing 50% HS and 50% LS, Af, isomers. The single-crystal structural analysis... 

Design, synthesis and structure determination of molecules, the skeletons of which are distorted by steric congestion and/or by charge perturbation, therefore, has become an additional research project of the Frankfurt group since 1989 [2,3]. Of the altogether about 100 single crystal structures determined in the meantime, about a dozen are of silicon organic compounds [5] (cf. examples in Fig. 1). 

Figure 5. Single crystal structures of (A) Tetrakis- and (B) N,N -Bis(trimethylsilyl))-p-phenylene-diamine with essential bond lengths, bond angles and non-bonded distances as well as van der Waals contours.

The existence of two polymorphs was reported for a NO-releasing derivative of acetyl-salicylic acid [28]. Selection crystallization of one form or the other was achieved from a number of solvent systems (14 solvents and 3 preparative methods), but several systems were identified that yielded mixtures of the two forms. The single-crystal structure of Form I was reported, but the habit of the Form II crystals precluded their characterization. The transition point of the two forms was calculated from intrinsic dissolution data to be higher than the melting points of both polymorphs and thus the two forms bear a monotropic relationship. 

In a continuous effort to circumvent the problem of poor solubility and tune the steric effects and electronic features of Pcs, several effective strategies have been developed. As a result, in recent years many neutral Pcs containing substituents at peripheral a or p positions, or in the axial direction, as well as ionic and sandwich-type Pcs have been synthesized and their single-crystal structures resolved by X-ray diffraction analysis [15-24], It therefore appears necessary to give a relatively comprehensive overview of the new progress in Pc chemistry. In this chapter, we summarize recent research results on the synthesis, crystal structures, and various physical properties of monomeric Pc compounds. 

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