The [2]rotaxanes were coordinated to a dodecametallic nickel(II) ring [Ni12(chp)12(O2CMe)12(H2O)6(THF)6] [2(THF)6] (Hchp = 6-chloro-2-hydroxypyridine) (Figure ) which has Ni II sites at the corners and midpoints of the edges of a hexagon. [2(THF)6] is insoluble in any solvent but dissolves in toluene at 60 °C in the presence of six equivalents of 1X to give a series of [7]rotaxanes, [2(1X)6]. Crystallography shows that in each compound the six [2]rotaxanes bind to the nickel(II) sites at the corners of the hexagon (Figure ). Within the central {Ni12} ring the Ni•••Ni edges are alternately bridged in two distinct ways; one edge is bridged by two µ2-O donors from chp -and a bridging acetate that lies within the ring. The second edge is bridged by a µ2-water and a µ2-O from acetate and a bridging acetate that lies outside the ring. The THF attached to 2 is displaced by 1X in each case and the structures of 1X are unchanged on binding. For molecule [2(1C)6] the structure of the central {Ni12} ring subtly changes during the coordination of [2]rotaxane 1C. Four of the six external acetate bridging ligands are displaced with pivalate ligands. Ligand exchange from the surrounding {Cr7Ni} rings is the likely source of the pivalate ligands on the central {Ni12} ring. The exact location of the exchanged pivalate ligands are well localised and are two well exposed easily accessible sites that are not involved in any μ2-O-bridging . For structure [2(1A)6] a chp ligand has been exchanged with an acetate ligand, although the extent of this substitution disorder is difficult to setermine crystallographically; one one site could be satisfactorily modelled as disordered, but all of the sites show some evidence of substitution. The conformations of the [7]rotaxanes in the crystal vary: we give three ranges in Table and more detail in Table . The {Cr7Ni} ring centroid to the Ni II site of 2 to which it is bound via the thread is fairly consistent within each [7]rotaxane, and is dependent on chain length of the thread, and the substitution measured. Similar variations are also seen in the angle that the thread itself makes with respect to the mean plane of 2 (Table ) and in the angle between the planes of the {Cr7Ni} rings and the {Ni12} ring.