Multilamellar liposomes of dipalmitoylphosphatidylcholine (DPPC) in solution with DNA and bivalent metal cations (Ca2+, Mn2+, Mg2+) self-assemble into a ternary DPPC-DNA-Me2+ complex. The supramolecular structure of the complex consists of an ordered multilamellar assembly where hydrated DNA helices are sandwiched between the lipid bilayers and the metal cations bind the phosphate groups of DNA to the lipid polar heads. In the range of explored incubation times, the complex coexists with the uncomplexed DPPC over the whole temperature range investigated (20-55 degrees C). Accordingly, two distinct coexisting lamellar phases are observed, one corresponding to the ternary complex and the other to the uncomplexed lipid. The structure and thermotropic phase behavior of both of these have been investigated by means of synchrotron X-ray diffraction, and the relevant structural data are deduced from experimental electron density profiles. While the uncomplexed lipid exhibits the same phase behavior as pure DPPC, that is, L-beta'-P-beta'-L-alpha, the thermotropic behavior of the bound lipid in the complex is partially altered. This is manifested as an increase in the main transition temperature and the disappearance of the ripple phase leading to the single L-beta'(c)-L-a(c) phase transition. The role of the different metal cations in promoting and stabilizing the DNA condensation into the ternary complex is also discussed.