title: Crystal structure and dynamic properties of a bimetallic cyano complex Cd(C4H8O2)Cu(CN)3 with an interpenetrating 3D framework containing a 1,4-dioxane bridging ligand as a rotor.
abstract: The title complex Cd(C(4)H(8)O(2))Cu(CN)(3) has a 3D twofold interpenetrating framework structure. The structural base of the framework is a planar hexagonal network complex of [Cu(CN)(3)Cd](infinity) ,which is formed with cyanides connecting the coordination sites of Cu(i) ions with a triangle planar form and the equatorial coordination sites of Cd(ii) ions with a trigonal bipyramid form. The networks are stacked and a 1,4-dioxane molecule coordinates to two Cd(ii) ions in alternate networks as a bridging ligand. The 1,4-dioxane ligand penetrates a hexagonal window of the network sandwiched between the bridged networks. This 1,4-dioxane bridge completes the 3D twofold interpenetrating framework structure. (2)H-NMR powder patterns of the deuterated complex Cd(C(4)D(8)O(2))Cu(CN)(3) revealed the dynamics of the 1,4-dioxane bridge as a rotor. Above 253 K, the 1,4-dioxane ligand undergoes rotational motion combined with a ring inversion between two chair conformations. The free energy of activation DeltaG(double dagger) for the ring inversion was calculated to be 41.4(7) kJ mol(-1) at 298 K.
authors.affiliation: Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro, Tokyo 153-8902, Japan. cnskor@mail.ecc.u-tokyo.ac.jp.
authors.forename: Naoki
authors.initials: N
authors.lastname: Sato
authors.forename: Shin-Ichi
authors.initials: S
authors.lastname: Nishikiori