Ethane-1,2-diphosphonic acid as a building block in supramolecular chemistry; a pillared-layer framework and framework-encapsulated cations

The 1:1 adduct of piperazine and ethane-1,2-diphosphonic acid is a salt [C(4)H(12)N(2)](2+).[C(2)H(6)O(6)P(2)](2-), in which both ions lie across centres of inversion in space group P2(1)/c. The anions are linked by a single type of O-H...O hydrogen bond [O...O, 2.562 (3) A; H...O, 1.73 A, O-H...O, 169 degrees ] into (6, 3) nets built from a single type of R(4)(4)(22) ring. The cations lie between these nets, linked to them by two types of N-H...O hydrogen bond [N...O, 2.635 (3) and 2.735 (3) A; H...O 1.72 and 1.82 A, N-H...O, 175 and 177 degrees ] such that the cations link adjacent sheets, thus forming a pillared-layer framework. The aquated adduct formed between trimethylenedipiperidine and ethane-1,2-diphosphonic acid is also a salt [C(13)H(28)N(2)](2+).[C(2)H(6)O(6)P(2)](2-).2.8[H(2)O], in which there are 12 different types of hydrogen bond, eight O-H...O and four N-H...O. The anions are linked into chains by pairs of O-H...O hydrogen bonds and these chains are linked by the water molecules into a continuous three-dimensional framework. Within the anion/water framework are large voids which contain pairs of cations, linked to the framework by N-H...O hydrogen bonds.