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

The novel organic–organometallic crystalline compounds [(η5-C5H5)2Co]­[(cis-deccaH)­(cis-deccaH2)] (1), [(η5-C5H5)2Co]­[(cis-deccaH)­(cis-deccaH2)]·H2O (2), [(η5-C5H5)2Co]­[trans-deccaH] (3), [(η5-C5H5)2Co]­[(trans-deccaH)­(trans-deccaH2)] (4), [(η5-C5Me5)2Co]­[cis-deccaH] (5), [(η5-C5Me5)2Co]­[trans-deccaH]·4H2O (6), and [(η6-C6H6)2Cr]­[trans-deccaH] (7) have been prepared by direct reaction of neutral [(η5-C5H5)2Co], [(η5-C5Me5)2Co], and [(η6-C6H6)2Cr] with the organic compounds cis-9,10-dihydroanthracene-9,10-α,β-succinic acid anhydride and trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (cis-decca and trans-deccaH2, 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.