By Gould R.F. (ed.)
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Extra resources for Nonstoichiometric Compounds
E. O±H or N±H, that can form hydrogen bonds with energies typically in the 4±15 kcal/mol range depending on the acceptor group employed. Such groups are common constituents of organic functional groups and thus can be incorporated into a wide range of inorganic building blocks based upon coordination compounds or organometallic compounds. 1, the dominant role of the metal in terms of hydrogen bond formation arises form its strong electronic in¯uence upon the donor or acceptor ability of the groups participating in hydrogen bonding.
The hydrogen-bonded square grid network is related to analogous coordination networks made using tetra-4pyridylporphyrin in the same manner that assemblies III and V are related [67a]. The groups of Suslick and Aoyama have prepared metalloporphyrin-based hydrogen-bonded networks using resorcinol-substituted porphyrins that stack into in®nite columns though O±H Á Á Á O hydrogen bonds between hydroxyl groups . Hydrogen Bonds: Application to Crystal Design 33 Figure 25 Structure of [Co(terpy-NH)2 ](PF6 )2 showing assembly of cationic cobalt complexes by self-complimentary N±H Á Á Á N hydrogen bonds (top, middle) to give a 2D grid (bottom).
16 Crystal Design: Structure and Function ligands, while cooperativity is less pronounced for the more isotropic ¯uoride ligands . In crystal engineering terms, this directly con®rms the importance of the suggested supramolecular synthons I  and II [41a] (Figure 8). Figure 9 illustrates a crystal design strategy  based upon these synthons in which bifurcated or trifurcated acceptor sites associated with perhalometallate anions are populated X X M H D D H X (D = C, N , O) I M X X II Figure 8 Supramolecular synthons D±H Á Á Á X2 M and D±H Á Á Á X3 M.