Iridium(III) amine complexes as high-stability structure-directing agents for the synthesis of metal phosphates

The metal complexes Ir(en)(3)(3+) and M((+/-)chxn)(3)(3+) (en = 1,2-diaminoethane, chxn = trans-1,2-diaminocyclohexane, M = Kr or Co) have been used to synthesize the layered compound Delta,Lambda-Ir(en)(3)[Al3P4O16]. xH(2)O (x approximate to 3.45) and the chain compounds M(chxn)(3)[Al2P3O12]. xH(2)O (x approximate to 4). The chain compounds contain two of the eight possible isomeric forms of the cation, Lambda(lel(2)ob)-[M(S,S-chxn)(2)(R,R-chxn)](3+) and its mirror image Delta(lel(2)ob)-[M(R,R-chxn)(2)(S,S-chxn)](3+). Microcrystals of the Ir(en)(3)(3+) and Ir(chxn)(3)(3+) containing AlPOs were structurally characterized using synchrotron radiation. Delta,Lambda-Ir(en)(3)[Al3P4O16]. xH(2)O is isomorphous with the previously reported material Delta,Lambda-Co(en)(3)[Al3P4O16]. xH(2)O. The materials prepared using Co((+/-)chxn)(3)(3+) and Ir((+/-)chxn)(3)(3+) are also isostructural with one another and contain a new type of aluminophosphate chain. The use of Ir(III) in the structure-directing metal complex enabled the use of much harsher hydrothermal conditions for the metal phosphate synthesis than could be employed with the corresponding Co(III) complexes. Ir(C2N2H8)(3)[Al3P4O16]. 3.45H(2)O: M-r = 895.5, orthorhombic, Pnna, a = 8.548(5), b = 21.983(14), c = 13.970(9) Angstrom, V = 2625(3) Angstrom(3), Z = 4, rho(calc) = 2.266 g cm(-3), lambda = 1.1167 Angstrom, mu = 14.03 mm(-1), F(000) = 1762, T = 293 K, R-F = 0.128 for 954 reflections I > 2 sigma(I). Ir(C6N2H14)(3)Al2P3O12. 4H(2)O: M-r = 945.7, triclinic, P (1) over bar, a = 9.649(5), b = 12.365(9), c = 16.083(8) Angstrom, alpha = 100.02(6), beta = 101.64(5), gamma = 104.75(6)degrees, V = 1765(2) Angstrom(3), Z = 2, rho(calc) = 1.779 g cm(-3), lambda = 1.1167 Angstrom, mu = 9.747 mm(-1), F(000) = 952, T = 293 K, R-F = 0.128 for 966 reflections I > 2 sigma(I).