In order to stabilise six-membered alicyclic ether guests through a hydrogen bond with an H 2 O ligand in the host, Hofmann-H 2 O-type [Cd(H 2 O) 2 Ni(CN) 4 ] and Hofmann-H 2 O-Td-type [Cd(H 2 O) 2 Cd(CN) 4 ] hosts were examined for accommodating 1,4-dioxane and morpholine as probable guests. The single crystal structures of the eventually obtained morpholine-ligated complex [Cd(C 4 H 9 NO) 2 Ni(CN) 4 ] (1) and 1,4-dioxane-guest clathrates, [Cd(H 2 O) 2 Ni(CN) 4 ] 2C 4 H 8 O 2 (2) and [Cd(H 2 O) 2 Cd(CN) 4 ] 2C 4 H 8 O 2 (3), are closely related in topology with previously known [Cd(py) 2 Ni(CN) 4 ], [Cd(NH 3 ) 2 Ni(CN) 4 ] 2C 4 H 8 O 2 and [Cd(NH 3 ) 2 Cd(CN) 4 ] 2C 6 H 6 , respectively, but involve hydrogen bonds between the morpholine ligands in 1, and between the aqua ligand of the host and the guest 1,4-dioxane in 2 and 3. Complex 1 crystallises in the orthorhombic system, Pmna, a = 7.985(1), b = 6.695(2), c = 14.314(2) 9, Z = 2, R = 0.048 for 1240 reflections; clathrate 2: monoclinic, P2/m, a = 7.3980(8), b = 7.6454(6), c = 8.0639(9) 9, β = 93.703(9)°, Z = 1, R = 0.041 for 1040; 3: monoclinic, C2/c, a = 12.054(5), b = 11.334(6), c = 15.249(2) 9, β = 91.62(2)°, Z = 4, R = 0.043 for 2129. The structure of a Hofmann-H 2 O-type hydrate [Fe(H 2 O) 2 Ni(CN) 4 4H 2 O, orthorhombic Pnma, a = 12.200(2), b = 14.028(2), c = 7.2327(9) 9, Z = 4, R = 0.042 for 710, is also reported.