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The new inclusion compound [(CH3)2NH2][CuZn(CN)4]º nH2O, whose host is a 3-D coordination polymer net formed with tetrahedral Cu(I) and Zn(II), as well as bridging cyanido ligands, exhibited a new type of structural transformation upon desorption/absorption of the guest water. This consisted of a reversible reconstruction of the host between a cristobalite-like and tridymite-like net. 63Cu solid-state NMR showed the conservation of the orientation of the cyanido bridges during the structural transformation, which required the breaking and reforming of the coordination bonds. [ABSTRACT FROM AUTHOR]