A family of organic-inorganic wheel-and-axle diols (Pd(LOH)(2)Cl(2), Pd(LOH)(2)(CH(3))Cl, Pd(LOH)(2)(CH(3)COO)(2), LOH = alpha-(4-pyridyl)benzhydrol) and several corresponding solvates are synthesized and characterized by single-crystal X-ray diffraction analysis. Their structures are compared to investigate the factors governing the modes of solid state association, the propensity to clathration, and the structural basis of guest inclusion. In all the complexes, the palladium coordination is a slightly distorted square. The LOH ligands coordinate Pd(2+) by means of the 4-pyridyl ring. In the chloride complexes solvation occurs with a 1:2 host/guest ratio by hydrogen bonding between the terminal -OH groups of the complex diol and one acceptor atom on the guest, and it is further assisted by guest stacking between host aryl rings. All solvates are organized in layers with practically invariant metrics, while the layers may be assembled in different arrangements. The structures of the nonsolvate compounds are related to the metrics of the solvate forms by rotation of the complex molecules within the layer plane. In all cases the nonsolvates are completely converted into the corresponding crystalline solvate forms by exposure to the vapor of the guest, and conversely they are quantitatively recovered from the solvate upon removal of the guest by mild conditions. On the basis of the structural data, it is proposed that the solvation/desolvation process proceeds by a concerted rotation of the complex molecules in the layer plane. The structural analysis of Pd(LOH)(2)(CH(3)COO)(2) and of its tetrahydrofuran monosolvate form suggests that the first step of the solid/gas solvation process may imply the clathration of 1 mol of guest between the aryl rings, which successively triggers the collective reorientation of the host molecules.

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The two complexes [Ag(LOH) 2 ]BF 4 and [Ag(LOH) 2 ]PF 6 are synthesised by reacting a-(4-pyridyl)benzhydrol (LOH) with [Ag(CH 3 CN) 4 ]BF 4 and AgPF 6 , respectively. Their solid state arrangements are reported and analyzed. The two structures are based on the combination of coordination bonds and non-covalent interactions. The silver ions are coordinated by two pyridine rings giving the wheel-and-axle Ag(LOH) 2 1 complex; the anions bridge the cations by means of hydrogen bonds with the OH groups: the result is a hybrid organic/inorganic hydrogen bonded network. A hierarchy in the importance and robustness of the supramolecular motifs observed in the two compounds is established, and the structural role of the anions is discussed.

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