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

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 Cu-3[NH2(CH2PO3)(2)](2) (1) crystallizes in the orthorhombic space group Pbca, with unit cell parameters a = 9.4430(10) Angstrom, b = 9.3681(10) Angstrom, c = 16.0755(17) A, V = 1422.1(3) Angstrom(3), 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 threedimensional 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 Co-3[NH2(CH2PO3)(2)](2) (2) crystallizes in the orthorhombic space group P2(1)2(1)2 with unit cell parameters a = 10.7346(8) Angstrom, b = 13.3704(10) Angstrom, c = 5.3699(4) Angstrom, V = 770.72(10) Angstrom(3), and Z = 2. All Co(II) ions are in a tetrahedral environment with both ends of the ligand bound via 0 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 P2(1)/ n, with unit cell parameters a = 7.3668(11) Angstrom, b = 8.1540(12) Angstrom, c = 14.090(2) Angstrom, beta = 103.935(2)degrees, V = 821.4(2) Angstrom(3), 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.