Inorganic Chemistry, Vol.40, No.15, 3745-3754, 2001
Solid-state coordination chemistry: Structural influences of copper-phenanthroline subunits on oxovanadium organophosphonate phases. Hydrothermal synthesis and structural characterization of the two-dimensional materials [Cu(phen) (VO)(O3PCH2PO3)(H2O)], [{Cu(phen)}(2)(V2O5) (O3PCH2CH2PO3)], and [{Cu(phen)}(2)(V3O5)(O3PCH2CH2CH2PO3)(2)(H2O)] and of the three-dimensional phase [{Cu(phen)}(2)(V3O5) (O3PCH2PO3)(2)(H2O)]
The hydrothermal reactions of CuCl2. 2H(2)O, Na3VO4, 1,10-phenanthroline, and the appropriate organodiphosphonate ligand yield [Cu(phen)(VO)(O3PCH2PO3)(H2O)] (1), [{Cu(phen)}(2)(V2O5)(O3PCH2CH2PO3)] (2), [{Cu(phen)}(2)(V3O5)(O3PCH2CH2CH2PO3)] (H2O)]; (3) and [{Cu(phen)}(2)(V3O5)(O3PCH2PO3)(2)(H2O)] (4). Compounds 1-3 exhibit two-dimensional structures. The structures exhibit distinct vanadium building blocks: square pyramidal, mononuclear V(IV) Sites in 1, a binuclear unit of corner-sharing V(V) tetrahedra in 2, and a trinuclear unit of corner-sharing V(V) square pyramids and a V(IV) octahedron in 3. The network structures of 1 and 2 are constructed from one-dimensional oxovanadium-diphosphonate chains linked by Cu(ll) square pyramids into two-dimensional layers. In contrast, compound 3 exhibits a two-dimensional oxovanadium-organodiphosphonate network, with Cu(II) sites decorating the surfaces. Compound 4 is unique in exhibiting a framework structure, which may be described as a three-dimensional oxovanadium-organodiphosphonate substructure with {Cu(phen)}(2+) subunits covalently attached to the surface of channels running parallel to the a-axis. The magnetic properties of 1-4 are also correlated to the structural characteristics. The magnetic behavior of 2 is thus dominated by antiferromagnetic interactions. The magnetic behavior of 1 and 4 is consistent with the presence of two distinct paramagnetic metal ions, Cu(LI) and V(IV). In contrast, 3 does not exhibit ferrimagnetic behavior, but rather weak antiferromagnetic coupling. Crystal data: 1,C13H10N2CuP2VO8, monoclinic P2(1)/c, a = 9.0656(5) Angstrom, b = 8.6584(5) Angstrom, c = 20.934(1) Angstrom, beta = 97.306(1)degrees, Z = 4; 2, C26H20N4Cu2P2V2O11, triclinic P (1) over bar, a = 10.6096(5) Angstrom, b = 11.6951(5) Angstrom, c = 13.1796(6) Angstrom, a = 71.369(1)degrees, beta = 70.790(1)degrees, gamma = 80.738(1)degrees, Z = 2; 3, C30H28N4Cu2P4V3O18, triclinic P (1) over bar, a = 9.4356(6) Angstrom, b = 10.6556(6) Angstrom, c = 11.0354(7) Angstrom, alpha = 118.187(1)degrees, beta = 91.416(1)degrees, gamma = 107.821(1)degrees, Z = 1; 4, C26H20N4Cu2P4V3O18, monoclinic, P2(1)/c a = 8.3947(3) Angstrom, b = 16.8401(7) Angstrom, c = 11.9144(5) Angstrom, beta = 93.903(1)degrees, Z = 2.