The First Organically Templated Layered Cobalt Phosphates: Hydrothermal Syntheses and Crystal Structures of [H3N(CH2)3NH3]0.5[Co(PO4)]·0.5H2O and [H3N(CH2)4NH3]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)3NH3]0.5[Co(PO4)]·0.5H2O (1) was prepared hydrothermally at 170°C over 48 h from an aqueous solution of CoCl2·6H2O, 1,3-diaminopropane, H3PO4(85%), and H2O in the mole ratio 1:7.2:4:444. Phosphate 2, [H3N(CH2)4NH3]0.5[Co(PO4)], was prepared in an analogous fashion from a mixture of CoCl2·6H2O, 1,4-diaminobutane, H3PO4(85%), (n-C4H9)4NOH, and H2O in the mole ratio 1:4:3.5:3:444 heated at 170°C for 47 h, to give brilliant blue plates in 70% yield. Crystal data for [H3N(CH2)3NH3]0.5[Co(PO4)]·0.5H2O (1): orthorhombicCmc21,a= 22.663(3)Å,b= 7.6255(8)Å,c= 6.7676(7)Å,V= 1174.7(6)Å3,Z= 8,dcalc= 2.273 g cm−3; structure solution and refinement based on 507 reflections withI0≥ 3σ (I0) (MoKα radiation, λ = 0.71073Å) converged atR= 0.030. Crystal data for [H3N(CH2)4NH3]0.5[Co(PO4)] (2): monoclinicP21/a,a= 7.508(3)Å,b= 23.655(4)Å,c= 6.775(1)Å, β = 90.55(2)°,V= 1203.3(5)Å3,Z= 8,dcalc= 2.185 g cm−3; structure solution and refinement based on 1305 reflections withI0≥ 3σ (I0) (MoKα, λ = 0.71073Å) converged atR= 0.048. Magnetization measurements indicate that 2 orders to a weak ferromagnetic state near 25 K.