Solid state coordination chemistry of the oxovanadium-diphosphonate/copper-bipyrimidine system: Crystal structures of [{Cu_2(bpyr)}VO(H_20)(HO_3PCH_2P0_3)_2] and [{Cu_2(bPyr)}{Cu_2(bpyr)(H_2O)_2}(VO_2)_2(HO_3PCH_2PO_3)_2(HO_3PCH_2PO_3H)_2]

摘要

Hydrothermal chemistry has been exploited in the preparation of two materials of the copper(II)-bipy_rimidine/oxovanadium-organophosphonate family, the two dimensional [{Cu(bpyr)}VO(H_20)_(H0_3PCH_2P0_3)_2] (1) and the three-dimensional [{Cu_2(bpyr)}{Cu_2(bpyr)(H_20)_2}(V0_2)_2(H0_3PCH_2P0_3)_2(H0_3PCH_2P0_3H)_2]_2H_20 (2_2H_20) (bpyr = 2,2'-bipyrimidine). The structure of 1 may be described as [{Cu_2(bpyr)}{Cu_2(bpyr)0_4}~(4n+)_n chains linked through {VO~(IV)(H_20)(H0_3 PCH_2P0_3)_2}~4- units. In contrast, the structure of 2 consists of {Cu_2(bpyr)}~(2+), {Cu_2(bpyr)(H_20)_2}~(2+) and {V~V0_2(HO_3PCH_2PO_3)-(HO_3PCH_2P0_3H)}~4- subunits linked into a framework architecture. The vanadium component of the reaction mixture failed to incorporate into the two-dimensional structure of [{Cu(bpyr)(H_2O)_2}{H0_3PCH_2CH_2PO_3H}_2](3). The architecture of 3 consists of '4+2' distorted octahedral Cu(II) sites linked through bpyr and diphosphonate ligands into a network. [Cu_2(bpyr)Cl_2] (4) is a simple one-dimensional ribbon constructed from parallel {CuCI}_n chains linked by bpyr ligands.