The first organically templated layered cobalt phosphates: Hydrothermal syntheses and crystal structures of [H3N(CH2)(3)NH3](0.5)[Co(PO4)]center dot 0.5H2O and [H3N(CH2)(4)NH3](0.5)[Co(PO4)]

The first organically templated layered cobalt phosphates have been prepared and structurally characterized by single crystal X-ray diffraction. The layered cobalt phosphate [H3N(CH2)(3)NH3](0.5)[Co(PO4)]. 0.5H(2)O (1) was prepared hydrothermally at 170 degrees C over 48 h from an aqueous solution of CoCl2 . 6H(2)O, 1,3-diaminopropane, H3PO4 (85%), and H2O in the mole ratio 1: 7.2 : 4 : 444. Phosphate 2, [H3N(CH2)(4) NH3](0.5)[Co(PO4)], was prepared in an analogous fashion from a mixture of CoCl2 . 6H(2)O, 1,4-diaminobutane, H3PO4 (85%), (n-C4H9)(4)NOH, and H2O in the mole ratio 1 : 4 : 3.5 : 3 : 444 heated at 170 degrees C for 47 h, to give brilliant blue plates in 70% yield. Crystal data for [H3N(CH2)(3)NH3](0.5)[Co(PO4). 0.5H(2)O (1): orthorhombic Cmc2(1), a = 22.663(3) Angstrom, b = 7.6255(8) Angstrom, c = 6.7676(7) Angstrom, V = 1174.7(6) Angstrom(3), Z = 8, d(calc), = 2.273 gcm(-3); Structure solution and refinement based on 507 reflections with I-0 greater than or equal to 3 sigma(I-0) (MoK alpha radiation, lambda = 0.71073 Angstrom) converged at R = 0.030. Crystal data for [H3N(CH2)(4)NH3](0.5)[Co(PO4)] (2): monoclinic P2(1)/a, a = 7.508(3) Angstrom, b = 23.655(4) Angstrom, c = 6.775(1) Angstrom, beta = 90.55(2) degrees, V = 1203.3(5) Angstrom(3), Z = 8, d(calc) = 2.185 gcm(-3); structure solution and refinement based on 1305 reflections with I-0 greater than or equal to 3 sigma (I-0) (MoK alpha, lambda = 0.71073 Angstrom) converged at R = 0.048. Magnetization measurements indicate that 2 orders to a weak ferromagnetic state near 25 K. (C) 1996 Academic Press,Inc.