Four-component intergrowth structures of the metal-ion cage complexes fac-(1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosane)MII diperchlorate hydrate, [M(C22H48N6)](ClO4)2.xH2O, M = Ni, Zn

The crystal structures of (1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo [7.7.7]tricosane-kappa(6)N,N',- N ",N"',N"",N""')nickel(II) diperchlorate-x(water) (x = 0.530), [Ni(C22H48N6)](ClO4)(2). 0.530H(2)O, and (1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo- [7.7.7]tricosane-kappa(6)N,N',N ",N"',N"",N""')zinc(II) diperchlorate-x(water) (x = 0.608), [Zn(C22H48N6)](ClO4)(2).-. 0.608H(2)O, are isomorphic and each is described as an intergrowth of four substructures, consistent with different modulations of an idealized parent structure of space group C2/c. Two substructures correspond to alternative orientations of a C (1) over bar structure for which x = 0 in the general formula [M(C22H48N6)](ClO4)(2). xH(2)O. and two substructures correspond to alternative origins of a P2(1)/n structure for which x = 1. Twinning also occurs. An analysis of the pseudosymmetry, a description of the refinement and a description of the refined structures are presented. The MN6 coordination geometry is essentially octahedral, in contrast to the trigonal-prismatic geometry observed for the Cd-II and Hg-II complexes of the same ligand.