Two solvatomorphic forms of a copper complex formulated as Cu(L(1))(ClO4)2·1.2H2O and Cu(L(1))(ClO4)2, where L(1) is 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane.

Two copper complex solvatomorphs, namely (3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II) 1.2-hydrate, [Cu(ClO4)2(C18H40N4)]·1.2H2O, (I), and (3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II), [Cu(ClO4)2(C18H40N4)], (II), are described and compared with each other and with a third, already reported, anhydrous diastereomer, denoted (III).

5,7,7,12,14,14-Hexamethyl-4,11-diaza-1,8-diazo-niacyclo-tetra-decane bis-(perchlorate) monohydrate.

In the title hydrated salt, C(16)H(38)N(4) (2+)·2ClO(4) (-)·H(2)O, the dication is protonated at the diagonally opposite N atoms proximate to the -C(CH(3))(2)- groups. Within the cavity, there are two ammonium-amine N-H⋯N hydrogen bonds. Supra-molecular layers are formed in the crystal packing whereby the water mol-ecule links two perchlorate anions, and the resultant aggregates are connected to the dications via N-H⋯O hydrogen bonds.

cis-(Acetato-κ(2)O,O')(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κ(4)N,N',N'',N''')nickel(II) perchlorate monohydrate.

The complete cation in the title hydrated mol-ecular salt, [Ni(CH(3)CO(2))(C(16)H(36)N(4))]ClO(4)·H(2)O, is generated by the application of crystallographic twofold symmetry; the perchlorate anion and water mol-ecule are each disordered around a twofold axis. The Ni(II) atom exists within a cis-N(4)O(2) donor set based on a strongly distorted octa-hedron and defined by the four N atoms of the macrocyclic ligand and two O atoms of a symmetrically coordinating acetate ligand. In the crystal, hydrogen bonding (water-acetate/perchlorate O-H⋯O and amine-perchlorate N-H⋯O) leads to layers in the ab plane.

cis-(Nitrato-κ(2)O,O')(2,5,5,7,9,12,12,14-octa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane-κ(4)N,N',N'',N''')cadmium nitrate hemihydrate.

The Cd(II) atom in the title complex, [Cd(NO(3))(C(18)H(40)N(4))]NO(3)·0.5H(2)O, is coordinated within a cis-N(4)O(2) donor set provided by the tetra-dentate macrocyclic ligand and two O atoms of a nitrate anion; the coordination geometry is distorted octa-hedral. The lattice water mol-ecule is located on a twofold rotation axis.

[(4E,11E)-5,7,12,14-Tetra-benzyl-7,14-dimethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene]copper(II) bis(per-chlorate).

The complete cation in the title compound, [Cu(C(40)H(48)N(4))](ClO(4))(2), is generated by the operation of a crystallographic centre of inversion. The Cu(II) ion exists in a tetra-gonally distorted trans-N(4)O(2) coordination geometry defined by the four N atoms of the macrocyclic ligand and two weakly bound perchlorate-O atoms from two anions. The N-H atoms form intra-molecular N-H⋯O(perchlorate) hydrogen bonds.

trans-(5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-4,11-diene-κN,N',N'',N''')bis-(nitrito-κN)cobalt(III) perchlorate hemihydrate.

The asymmetric unit of the title Co(III) complex, [Co(NO(2))(2)(C(16)H(32)N(4))]ClO(4)·0.5H(2)O, comprises two complex cations, two perchlorate anions and a water mol-ecule of crystallization. The Co(III) atoms exist within distorted octa-hedral N(6) geometries defined by four N atoms of the macrocycle ligand and trans-N atoms derived from the nitrite anions.