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Metal—phenoxyalkanoic acid interactions. Part 14. The crystal and molecular structures of diaquabis(4-fluorophenoxyacetato)copper(II) bis(4-fluorophenoxyacetic acid)dihydrate and tetra-μ-(4-fluorophenoxyacetato-0,0′)-bis[(2-aminopyrimidine)copper(II)]
Authors:Eric J O&#x;Reilly  Graham Smith  Colin HL Kennard
Institution:Department of Chemistry, Queensland Institute of Technology, Brisbane, Qld., 4000 Australia;Department of Chemistry, University of Queensland, Brisbane, Qld., 4067 Australia
Abstract:The crystal structures of two copper(II) complexes of 4-fluorophenoxyacetic acid (4-FPAH) have been determined by X-ray diffraction. Cu(4-FPA)2(H2O)2]·2(4-FPAH)·2H2O (1) is triclinic, space group P1 with Z = 1 in a cell of dimensions a = 14.808(2), b = 9.832(2), c = 6.847(2) Å, α = 87.77(2), β = 98.41(2), γ = 112.33(2)° and was refined to a residual of 0.038 for 1697 ‘observed’ reflections. The coordination sphere in this complex is tetragonally distorted octahedral comprising two waters CuO, 1.940(3) Å], two unidentate carboxylate oxygens CuO, 1.942(2) Å] and two ether oxygens CuO, 2.471(2) Å]. Two adducted 4-FPAH] acid molecules are linked to the un-coordinated oxygens of the acid ligands by hydrogen bonds 2.547(4) Å]. Cu2(4-FPA)4(2-aminopyrimidine)2] (2) is triclinic, space group P1 with Z = 1 in a cell of dimensions a = 12.688(2), b = 11.422(2), c = 7.951(1) Å, α = 78.74(1), β = 107.51(1), γ = 75.78(1)°, and was refined to a residual of 0.042 for 2683 ‘observed’ reflections. (2) is a centrosymmetric tetracarboxylate bridged dimer with four similar CuO (equatorial) distances 1.967–1.987 Å; 1.977(3) Å mean] and the axial position occupied by the hetero nitrogen of the 2-aminopyrimidine ligand CuN, 2.176(3) Å]. The Cu---Cu separation is 2.710(1) Å. Crystal data are also presented which confirm the isostructurality of complex (2) with Cu2(phenoxyacetate)4(2-aminopyrimidine)2], the CoII, MgII and MnII4-fluorophenoxyacetate complexes with their phenoxyacetic and 4-chlorophenoxyacetic acid analogues, and of CdII4-fluorophenoxyacetate with CdII and ZnII phenoxyacetates.
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