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 [H 3 N(CH 2 ) 3 NH 3 ] 0.5 [Co(PO 4 )]·0.5H 2 O (1) was prepared hydrothermally at 170°C over 48 h from an aqueous solution of CoCl 2 ·6H 2 O, 1,3-diaminopropane, H 3 PO 4 (85%), and H 2 O in the mole ratio 1:7.2:4:444. Phosphate 2, [H 3 N(CH 2 ) 4 NH 3 ] 0.5 [Co(PO 4 )], was prepared in an analogous fashion from a mixture of CoCl 2 ·6H 2 O, 1,4-diaminobutane, H 3 PO 4 (85%), ( n -C 4 H 9 ) 4 NOH, and H 2 O 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 [H 3 N(CH 2 ) 3 NH 3 ] 0.5 [Co(PO 4 )]·0.5H 2 O (1): orthorhombic Cmc 2 1 , a = 22.663(3) A, b = 7.6255(8) A, c = 6.7676(7) A, V = 1174.7(6) A 3 , Z = 8, d calc = 2.273 g cm −3 ; structure solution and refinement based on 507 reflections with I 0 ≥ 3σ ( I 0 ) (Mo K α radiation, λ = 0.71073 A) converged at R = 0.030. Crystal data for [H 3 N(CH 2 ) 4 NH 3 ] 0.5 [Co(PO 4 )] (2): monoclinic P 2 1 / a , a = 7.508(3) A, b = 23.655(4) A, c = 6.775(1) A, β = 90.55(2)°, V = 1203.3(5) A 3 , Z = 8, d calc = 2.185 g cm −3 ; structure solution and refinement based on 1305 reflections with I 0 ≥ 3σ ( I 0 ) (Mo K α, λ = 0.71073 A) converged at R = 0.048. Magnetization measurements indicate that 2 orders to a weak ferromagnetic state near 25 K.