Zinc Diphosphonates Templated by Organic Amines: Syntheses and Characterizations of [NH<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>NH<sub>3</sub>]Zn(hedpH<sub>2</sub>)<sub>2</sub>·2H<sub>2</sub>O and [NH<sub>3</sub>(CH<sub>2</sub>)<i><sub>n</sub></i>NH<sub>3</sub>]Zn<sub>2</sub>(hedpH)<sub>2</sub>·2H<sub>2</sub>O (<i>n</i> = 4, 5, 6) (hedp = 1-Hydroxyethylidenediphosphonate)
收藏资源简介：
Four new zinc diphosphonate compounds with formulas [NH3(CH2)2NH3]Zn(hedpH2)2·2H2O, 1, [NH3(CH2)nNH3]Zn2(hedpH)2·2H2O, (n = 4, 2; n = 5, 3; n = 6, 4) (hedp = 1-hydroxyethylidenediphosphonate) have been synthesized under hydrothermal conditions at 110 °C and in the presence of alkylenediamines NH2(CH2)nNH2 (n = 2, 4, 5, 6). Crystallographic data for 1: monoclinic, space group C2/c, a = 24.7422(15), b = 5.2889(2), c = 16.0338(2) Å, β = 117.903(1)°, V = 1856.17(18) Å3, Z = 4; 2: monoclinic, space group P21/n, a = 5.4970(3), b = 12.1041(6), c = 16.2814(12) Å, β = 98.619(5)°, V = 1071.07(11) Å3, Z = 2; 3: monoclinic, space group P21/n, a = 5.5251(2), b = 12.5968(3), c = 16.1705(5) Å, β = 99.182(1)°, V = 1111.02(6) Å3, Z = 2; 4: triclinic, space group P-1, a = 5.4785(2), b = 14.1940(5), c = 16.0682(6) Å, α = 81.982(2)°, β = 89.435(2)°, γ = 79.679(2)°, V = 1217.11(8) Å3, Z = 2. In compound 1, two of the phosphonate oxygens are protonated. The metal ions are bridged by the hedpH22- groups through three of the remaining four phosphonate oxygens, forming a one-dimensional infinite chain. The protonated ethylenediamines locate between the chains in the lattice. In compounds 2−4, only one phosphonate oxygen is protonated. Compounds 2 and 3 have a similar three-dimensional open-network structure composed of {Zn2(hedpH)2}n double chains with strong hydrogen bonding interactions between them, thus generating channels along the [100] direction. The protonated diamines and water molecules reside in the channels. Compound 4 contains two types of {Zn2(hedpH)2}n double chains which are held together by strong hydrogen bonds, forming a two-dimensional network. The interlayer spaces are occupied by the [NH3(CH2)6NH3]2+ cations and water molecules. The significant difference between structures 2−4 is also featured by the coordination geometries of the zinc atoms. The geometries of those in 2 can be described as distorted octahedral, and those in 3 as distorted square pyramidal. In 4, two independent zinc atoms are found, each with a distorted octahedral and a tetrahedral geometry, respectively.
