Organic-organometallic crystal synthesis .2. Organic frameworks constructed around [(eta(5)-C5H5)(2)Co](+) via charge-assisted O-H center dot center dot center dot O and C-H center dot center dot center dot O hydrogen bonds

The engineering of organic-organometallic crystals based on strong O-H-O and charge-assisted C-H-O hydrogen bonds is discussed. The organic acids D,L- and L-tartaric acid (D,L-H(2)TA and L-H(2)TA) can be utilized to generate honeycomb-type organic frameworks around the organometallic cation [(eta(5)-C5H5)(2)Co](+). The crystalline products of chemical formulae [(eta(5)-C5H5)(2)Co](+)[(D,L-HTA)(D,L-H(2)TA)](-) (1) and [(eta(5)-C5H5)(2)Co](+)[L-HTA](-) (8) are, respectively, constituted of hexagonal and tetragonal superanions molded around the cobalticinium cations. On changing the stoichiometric ratio [(eta(5)-C5H5)(2)Co]/(D,L-H(2)TA) from 1:2 to 1:1, the crystalline material [(eta(5)-C5H5)(2)Co](+)[D,L-HTA](-). H2O (2) is produced while the undecahydrate crystalline material {[(eta(5)-C5H5)(2)Co](+)}(2)[L-BTA](2-). 11H(2)O (4) is obtained when the organic partner is dibenzoyl-L-tartaric acid (L-H(2)BTA). The use of chiral acids in the preparation of 2 and 4 provides a simple route to chiral crystals. The participation of water molecules in interactions of the C-H-O type is discussed. These results are used to put forward a practical design strategy far organometallic crystal engineering.