HYDROGEN-BONDED ADDUCTS OF FERROCENE-1,1'-DIYLBIS(DIPHENYLMETHANOL) -CRYSTAL AND MOLECULAR-STRUCTURES OF 1 1 ADDUCTS WITH 4,4'-BIPYRIDYL, PIPERAZINE AND DIMETHYLFORMAMIDE, THE 2/1/1 HYDRATED ADDUCT WITH MORPHOLINE, AND 2 ADDUCTS WITH 1,4-DIOXANE, 1/1 AT 150-K AND 1/2 AT 298-K/

Host-guest adducts formed by ferrocene-1,1'-diylbis(diphenylmethanol) 1 with oxygen-and/or nitrogen-containing guests exhibited a wide range of hydrogen-bonding patterns as determined by X-ray crystallography. The 1 : 1 adduct 2 formed with 4,4'-bipyridyl comprises a centrosymmet ric hydrogen-bonded aggregate involving two molecules of the diol and one of the bipyridyl and contains intramolecular O-H ... O and intermo lecular O-H ... N hydrogen bonds; the second molecule of the bipyridyl , also centrosymmetric, is trapped in a cavity, but is not hydrogen bo nded to any other part of the structure. The structure of the 1 : 1 ad duct formed with piperazine 3 is chiral and consists of infinite spira l chains, with alternating diol and piperazine molecules, which contai n only O-H ... N hydrogen bonds. Morpholine forms both anhydrous 4a an d hydrated adducts 4b with the host diol, both having host : guest rat ios of 2 : 1: the hydrated adduct contains infinite ribbons comprising ferrocene units on the outside edges and disordered water and morphol ine components in the body of the ribbon. With 1,4-dioxane a 1 : 1 5a and a 1 : 2 adduct 5b are formed. The centrosymmetric hydrogen-bonded aggregate of 5a consists of two molecules of the diol and one of dioxa ne and contains both intra- and inter-molecular O-H ... O hydrogen bon ds: the second dioxane molecule is also centrosymmetric and is trapped in a structural cavity and not bonded to the rest of the structure. A dduct 5b is isomorphous with the 1 : 2 diol : pyridine adduct. The dio l component lies on a two-fold rotation axis, forming hydrogen bonds t o the dioxane molecules which are highly disordered and readily lost f rom the structure. In the 1 : 1 complex formed with dimethylformamide 6 inter- and intra-molecular O-H ... O hydrogen bonds link a finite ho st-guest pair, which also includes an intermolecular C-H ... pi(arene) interaction. The hydrogen-bonding patterns are analysed and codified using a graph-set approach.