An X-ray diffraction study on the structures of monochloropentakis(N,N-dimethylformamide)copper(II), trichloromono(N,N-dimethylformamide)- and tetrachlorocuprate(II) complexes in N,N-dimethylformamide.

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The structure of the monochlorocopper(II), trichloro- and tetrachlorocuprate(II) complexes in N,N-dimethylformamide (DMF) has been studied by the X-ray diffraction method at 25 °C. The radial distribution curve obtained for a solution containing the monochlorocopper(II) complex as the predominant species reveals the presence of an axially elongated octahedral [CuCl(dmf)5]+ complex, three Cu–O(eq) and two Cu–O(ax) bond lengths being 199(1) and 239(4) pm, respectively. The chloride ion binds to the copper(II) ion at the equatorial site and the Cu–Cl distance is 220(2) pm. The Cu–O(eq) bond length within the [CuCl(dmf)5]+ complex is practically the same as that within the [Cu(dmf)6]2+ (203 pm). The X-ray scattering data of solutions containing the tri- and tetrachlorocuprate(II) complexes as the main species are well explained in terms of the existence of the distorted tetrahedral [CuCl3(dmf)]− and [CuCl4]2− complexes, respectively, in the solutions. The Cu–Cl and Cu–O bond lengths within the [CuCl3(dmf)]− complex are 219(1) and 230(13) pm, respectively. The Cu–O distance within the complex is longer than that of the equatorial Cu–O bond within the [Cu(dmf)6]2+ and [CuCl(dmf)5]+ ions. The Cu–Cl bond length within the [CuCl4]2− complex is 226(1) pm and is longer than that within the [CuCl3(dmf)]2− complex. The nonbonding Cl···Cl distances within the [CuCl4]2− complex are 346(3) and 412(6) pm.