The crystal supramolecularity of metal phenanthroline complexes
Abstract
The ) motifs, and less frequently edge-to-face (EF
) motifs. An investigation of the 335 M(phen) complexes, 159 M(phen)2 complexes, and 33 M(phen)3 complexes in the Cambridge Structural Database has revealed that in crystals these primary OFF and EF motifs combine to form concerted motifs, and extended motifs, in a variety of ways. Stacks of phen
) occurs for complexes M(phen)2 and M(phen)3, with some variety in geometry between a single OFF at one extreme to (EF
)2 at the other. This variability in the P4AE is a consequence of the larger surface area of the phen
), and has been evaluated by calculations of the supramolecular attractive energies. The P4AE associate further, maximising the use of phen surfaces, to form chains of P4AE, chains of P4AE·OFF, and compact two-dimensional nets propagated by both P4AE and OFF motifs. There are examples of three-dimensional nets using these motifs. There is a notable absence of sixfold
)6) amongst M(phen)3 complexes, and a clear difference with M(bipy)3 complexes where 6AEs are prevalent. Various M(phen)2 and M(phen)3 complexes pack in crystals to form tight hydrophobic domains, often as slabs, segregated from hydrophilic domains containing hydrogen bonding components and anions. The