SYNTHESIS, STRUCTURE, AND REACTIVITY OF SOME FUNCTIONALIZED ZINC AND COPPER(II) PHOSPHONATES

Functional analogues (R = (CH2)(2)CO2H, (CH2)(2)Br, (CH2)(2)NH3+NO3-) Of the two structural models, Zn-II(O-3-PR) .H2O and Cu-II(O(3)PR).H2O (R = n-alkyl, phenyl, were prepared in a mixture of acetone and water. Attempts to graft an aromatic amine on the carboxyl function of Zn(O3P(CH2)(2)CO2H).H2O led to the formation of Zn(O3P(CH2)(2)CO2H).0.5C(6)H(5)NH(2), Zn[Zn(O3P(CH2)(2)CO2)](2).3H(2)O and Zn-3(O3P(CH2)(2)CO2)(2) (monoclinic P2(1)/c (No. 14), a = 8.126(1) Angstrom, b = 9.2371(1) Angstrom, c = 8.587(2) Angstrom, beta = 106.26(3)degrees, Z = 2, R = 0.036, R(w) = 0.037). No amide formation was detected. However, the desired Zn(O3P(CH2)(2)CONHC6H5) product was directly synthesized, according to an original one-step procedure involving the three molecular precursors: zinc nitrate, (2-carboxyethyl)phosphonic acid and aniline. If aniline was replaced by sodium hydroxyde, a pillared layered phosphonate was obtained: Zn(O3P(CH2)(2)CO2H).1.5H(2)O (orthorhombic Pccn (No. 56), a = 9.885(1) Angstrom, b = 10.020(1) Angstrom, c = 16.438(3) Angstrom, Z = 8, R = 0.062, R(w) = 0.074).