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Syntheses, Structure, and Magnetic Properties of New Types of Cu(II), Co(II), and Mn(II) Organophosphonate Materials:  Three-Dimensional Frameworks and a One-Dimensional Chain Motif

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posted on 2004-08-10, 00:00 authored by Deyuan Kong, Yang Li, Xiang Ouyang, Andrey V. Prosvirin, Hanhua Zhao, Joseph H. Ross,, Kim R. Dunbar, Abraham Clearfield
The hydrothermal syntheses, structures, and magnetic properties of the Cu(II), Co(II), and Mn(II) complexes with organophosphonic acid H2O3PCH2NH2+CH2PO3H- are reported. Compound Cu3[NH2(CH2PO3)2]2 (1) crystallizes in the orthorhombic space group Pbca, with unit cell parameters a = 9.4430(10) Å, b = 9.3681(10) Å, c = 16.0755(17) Å, V = 1422.1(3) Å3, and Z = 4. The X-ray crystallographic determination reveals copper ions in two different coordination environments that are bridged by one terminal oxygen atom to form a three-dimensional framework of corner-sharing layers. Antiferromagnetic coupling between the two types of Cu units in 1 was observed at 15 K, followed by ferromagnetic ordering at 9 K. Compound Co3[NH2(CH2PO3)2]2 (2) crystallizes in the orthorhombic space group P21212 with unit cell parameters a = 10.7346(8) Å, b = 13.3704(10) Å, c = 5.3699(4) Å, V = 770.72(10) Å3, and Z = 2. All Co(II) ions are in a tetrahedral environment with both ends of the ligand bound via O atoms to adjacent Co(II) ions, thus creating tetranuclear 16-membered rings. Compound Mn{[NH2(CH2PO3H)2]2(H2O)2} (3) crystallizes in the monoclinic space group P21/n, with unit cell parameters a = 7.3668(11) Å, b = 8.1540(12) Å, c = 14.090(2) Å, β = 103.935(2)°, V = 821.4(2) Å3, and Z = 2. Four phosphate oxygen atoms and two water molecules are coordinated to the mononuclear octahedral Mn(II) ions. The amino groups are protonated and therefore do not coordinate to Mn(II). Compound 3 features a one-dimensional chain architecture stitched together by hydrogen bonds.

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