Diverse solid-state and solution structures within a series of hexaamine dicopper(II) complexes

Mono- and dicopper(II) complexes of a series of potentially bridging hexaam ine ligands have been prepared and characterized in the solid state by X-ra y crystallography. The crystal structures of the following Cu-II complexes are reported: [Cu(HL3)](ClO4)(3), C11H31Cl3CuN6O12, monoclinic, P2(1)/n, a = 8.294(2) Angstrom, b = 18.364(3) Angstrom, c = 15.674(3) Angstrom, beta = 94.73(2)degrees, Z = 4; {[Cu-2(L-4)(CO3)](2)}(ClO4)(4). 4H(2)O, C40H100Cl4 Cu4N12O26, triclinic, P (1) over bar, a = 9.4888(8) Angstrom, b=13.353(1) A ngstrom,. c = 15.329(1) Angstrom, alpha = 111.250(7)degrees, beta = 90.068( 8)degrees, gamma = 105.081(8)degrees, Z=1; [Cu-2(L-5)(OH2)(2)](ClO4)(4), C( 13)H(36)Cl(4)Cu(2)Z(6)O(18), monoclinic, P2(1)/c, a = 7.225(2) Angstrom. b = 8.5555(5) Angstrom, c = 23.134(8) Angstrom, beta = 92.37(1)degrees, Z = 2 ; [Cu-2(L-6)(OH2)(2)](ClO4)(4). 3H(2)O, C14H44Cl4Cu2N6O21, monoclinic, P2(1 )/a, a = 15.204(5) Angstrom, b = 7.6810(7) Angstrom, c = 29.370(1) Angstrom , beta = 100.42(2)degrees, Z = 4. Solution spectroscopic properties of the bimetallic complexes indicate that significant conformational changes occur upon dissolution, and this has been probed with EPR spectroscopy and molec ular mechanics calculations.