By Jenny P. Glusker (auth.), Prof. Dr. Edwin Weber, Y. Aoyama, M. R. Caira, G. R. Desiraju, J. P. Glusker, A. D. Hamilton, R. E. Meléndez, A. Nangia (eds.)
Considering the excessive point of our wisdom bearing on covalent bond formation within the natural chemistry of molecules, our figuring out of the rules keen on natural sturdy layout is sort of in its infancy. whereas chemists this present day may be able to synthesize natural molecules of very excessive complexity utilizing subtle tools of practise, they lack normal techniques allowing them to reliably are expecting natural crystalline or strong constructions from molecular descriptors - regardless of how uncomplicated they're. however, approximately all of the natural subject surrounding us isn't within the single-molecule kingdom yet aggregated and condensed to shape liquid or good molecular assemblages and structural arrays giving upward thrust to the appearances and homes of natural compounds we often notice. evidently, undefined, optical or magnetic homes of good natural fabrics which are very important requisites for destiny applied sciences and high-tech purposes, in addition to the steadiness and solubility habit of a medicament rely on the constitution of the molecule and the intramolecular forces, yet much more decisively at the intermolecular forces, i. e. the packing constitution of the molecules to which a common process is missing. this example involved ]. Maddox a few years in the past to this kind of measure that he defined it as "one of the continued scandals within the actual sciences" [see (1998) Nature 335:201; see additionally Ball, P. (1996) Nature 381:648]. the matter of predicting natural good and crystal constructions is especially dif- cult.
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Small, highly charged cations, such as Be2+ and Al3+ have low coordination numbers, although they are usually higher in crystals than in gases or liquids. Larger cations have higher coordination numbers, 6 being the most common value 33 Directional Aspects of Intermolecular Interactions found, but values may reach 12. Ionic radii vary with the coordination number . For example, a cation with a tetrahedral coordination of four anions has 93–95% the radius of the same cation with a coordination number of 6, but if the coordination number is 8, the radius is 103% that for coordination number 6.
26a–c. Motifs found in magnesium-binding proteins: a the ring noted in Fig. 24; b an aquated carboxylate motif; c stereoview of the motif found in cobalt formate . These motifs are also used by other metal ions that have similar sizes and ligand preferences Directional Aspects of Intermolecular Interactions 35 Fig. 27. Use of a motif to orient the magnesium octahedron in a protein (mandelate racemase) to facilitate a reaction . The motif in Fig. 26b serves to orient the direction in which substrate (modeled in this crystal structure by an inhibitor) binds in catalytic processes, with possible changes in coordination number during reaction.
31. Complexation of a metal ion (K+ of KSCN) by dibenzo-18-crown-6 . This stereo- view shows that the metal ion is not exactly in the plane of the complexing oxygen atoms gen atoms . Cram  and Lehn  made more complex molecules, designing them to perform certain functions with the specific aims of mimicking selective transport across biological membranes and certain aspects of enzyme chemistry. 6 Metal-Binding Sites in Proteins The experimental observation that there is a high probability that the metal ion lies in the plane of a neighboring carboxylate ion provides a mechanism for Directional Aspects of Intermolecular Interactions 39 searching for metal-binding sites in proteins.
Design of Organic Solids by Jenny P. Glusker (auth.), Prof. Dr. Edwin Weber, Y. Aoyama, M. R. Caira, G. R. Desiraju, J. P. Glusker, A. D. Hamilton, R. E. Meléndez, A. Nangia (eds.)