Although solution-based ligand exchange methods have been used to obtain heteroleptic porous coordination cages based on Cu(II), the poor solubility of the as-formed homoleptic cages [Cu4(CH3L)4]-DMA and [Cu4(MeOL)4]-DMA precluded that approach here. Instead, a given ratio of the ligands CH3LH2 and LH2, or CH3LH2 and MeOLH2, was reacted with Cu(OAc)2•H2O in dimethylacetamide (DMA) overnight at 80 °C, yielding single crystals of the complexes. In addition, we synthesised a new polymorph of the cage [Cu4(L)4]-DMA, using Cu(OAc)2•H2O as the metal source (Table ) -this cage had previously been reported in the space group P21/c when synthesised from CuCl2. For the cages [Cu4(MeOL)4-x(CH3L)x]-DMA (x = 1, 2, 3), the single crystal X-ray diffraction data were of sufficient quality to extract the unit cell parameters (Table ) and show the connectivity of the core of the lantern (Fig. ), but were too highly disordered to accurately model the positions of the methoxy-and methyl substituents of the cages, in common with other attempts to obtain scrambled metal-organic polyhedra. These scrambled cages crystallise in the monoclinic space group P21/n, as does the homoleptic cage [Cu4(CH3L)4]-DMA, but differing from the cage [Cu4(MeOL)4]-DMA (C2/c). All of the cages are neutral, formed by two [Cu2] paddlewheel nodes linked through four deprotonated organic linkers. As the crystallographic data were too disordered to resolve the positions of the methyl and methoxy-groups, IR spectroscopy was used to track the scrambling of the cages, illustrated by the decrease in the intensity of the stretch at 770 cm -1 as the The second family of scrambled cages based on varying ratios of CH3LH2 and LH2 were suitable for single-crystal X-ray analysis. Across the series [Cu4(L)4-x(CH3L)x]-DMA (x = 0, 1, 2, 3, and 4), all of the cages crystallise in the monoclinic space group P21/n. DMA molecules coordinate to the outer sites of the paddlewheel while water molecules are coordinated in the inner site of the paddlewheel (Fig. ). The asymmetric unit of each member of the family consists of one half of a cage, with two crystallographically independent positions for the ligands (Fig. ). Therefore, rather than occupying a unique position within the MOP, yielding an ordered heteroleptic cage of unique composition, the ligand CH3L 2-is split over both possible sites. It was possible to refine these occupancies, as shown in Fig. for the cage [Cu4(L)2(CH3L)2]-DMA, where the occupancy of one site by CH3L 2-is 64% and in the other it is 53%. Because of the previously mentioned poor solubility of the cages, solution-phase analysis techniques such as mass spectrometry were not possible to evaluate the relative populations of the distinct possible cage compositions. Based on the occupancies determined from the crystallographic data, the most probable composition of a cage in the material