Shape Takes the Lead: Templating Organic 3D-Frameworks around Organometallic Sandwich Compounds

The novel organic-organometallic crystalline compounds [eta(5)-C5H5)(2)Co][(cis-deccaH)(cis-deccaH(2))] (1), [(eta(5)-C5H5)(2)Co][(cis-deccaH)(cis-deccaH(2))]center dot H2O (2), [(eta(5)-C5H5)(2)Co][trans-deccaH] (3), [(eta(5)-C5H5)(2)Co][(transdeccaH)(trans-deccaH2)] (4), [(eta(5)-C5Me5)(2)Co][cis-deccaH] (5), [(eta(5)-C5Me5)2Co] [trans-deccaH]center dot 4H(2)O (6), and [(eta(6)-C6H6)(2)Cr][trans-deccaH] (7) have been prepared by direct reaction of neutral [(eta(5)-C5H5)(2)Co], [(eta(5)-C5Me5)(2)Co], and [(eta(6)-C6H6)(2)Cr] with the organic compounds cis-9,10-dihydroanthracene-9,10-alpha,beta-succinic acid anhydride and trans-9, 10-dihydro-9,10-ethanoanthracene-11,12-clicarboxylic acid (cis-decca and trans-deccaH(2), respectively). The organic building blocks have been chosen because of their three-stem star-like shape and the difference in hydrogen-bonding capacity. It is shown that the formation of a honeycomb-type anionic arrangement around the organometallic cations does not require the assistance of strong hydrogen-bonding interactions. Depending on the stoichiometric ratio and on the presence of water molecules, rectangular and layered crystal packings are also obtained.