A series of new copper complexes [(thd)Cu(OMe)]4 (4), [(hfd)Cu(OMe)]4 (5), [(hfd)Cu(OMe)]4 (6), [(thd)Cu-(OPri)]2 (7), [(tfd)Cu(OPri)]2 (8), [(thd)Cu(OPhf)]2 (9), [(tfd)Cu(OPhf)]2 (10), [(hfd)Cu(OPhf)]2 (11), [(thd)Cu(OCH2CH2OMe)]4 (12), [(tfd)Cu(OCH2CH2OMe)]4 (13), and [(hfd)Cu(OCH2CH2OMe)]4 (14) (where thd, tfd, and hfd are the 2,2,6,6-tetramethyl-3,5-heptanedionato-, 1, 1, 1-trifluoro-2,4-pentanedionato-, and 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato ligands, respectively) were synthesized by using a beta-diketonate/alkoxide exchange method. Compounds 6, 10, 12, 14 were characterized by single-crystal X-ray diffraction. 6 and 10 exist as labile THF adducts with four and two THF molecules coordinated to the Cu atoms, respectively. Complex 10 has a centrosymmetric dimeric structure, and complexes 6 and 14 (crystallographic D2 and C2 symmetry, respectively) represent a cubane-type tetranuclear structure, in which four expanded parallel Cu...O bonds are observed. Complex 12 (C(i) symmetry) also contains a tetranuclear unit but belongs to a group of ladderlike structures with two stronger and two weaker Cu...O contacts. Starting from 12, the mixed-metal complex 15 was obtained, which was characterized by X-ray single crystal diffractometry. Complex 15 contains one Ba and four Cu atoms and has approximate C2 symmetry. A unifying approach was applied for the description of the frameworks of 15, the related Ba, Cu complex 18, and the high-T(c) superconductor 19 in terms of common elementary building blocks. Crystallographic parameters: for 6, space group Fddd, a = 14.00 (1) angstrom, b = 27.75 (2) angstrom, c = 29.16 (1) angstrom, Z = 8, R = 0.0574, and R(w) = 0.0679 for 4492 reflections; for 10, space group P1BAR, a = 9.670 (2) angstrom, b = 10.054 (2) angstrom, c = 10.776 (3) angstrom, alpha = 107.00 (2)-degrees, beta = 92.15 (2)-degrees, gamma = 112.07 (2)-degrees, Z = 1, R = 0.0532, and R(w) = 0.0533 for 2818 reflections; for 12, space group P2(1)/n, a = 12.450 (5) angstrom, b = 15.573 (8) angstrom, c = 17.324 (9) angstrom, beta = 93.68 (4)-degrees, Z = 2, R = 0.0538, and R(w) = 0.0584 for 3515 reflections; for 14, space group C2/c, a = 17.046 (5) angstrom, b = 17.211 (5) angstrom, c = 17.634 (3) angstrom, beta = 93.50 (2)-degrees, Z = 4, R = 0.0599, and R(w) = 0.0575 for 2870 reflections; for 15, space group P1BAR, a = 14.285 (5) angstrom, b = 16.407 (5) angstrom c = 19.409 (6) angstrom, alpha = 77.57 (3)-degrees, beta = 89.60 (3)-degrees, gamma = 81.14 (3)-degrees, Z = 2, R = 0.0983, and R(w) = 0.0983 for 5579 reflections.
