Cyclam as a structure-directing agent in the crystallization of aluminophosphate open framework materials from fluoride media

Two aluminofluorophosphates ha,e been synthesized using 1,4,8,11-tetraazacyclotetradecane (cyclam) as a structure-directing agent (SDA). The two materials were synthesized hydrothermally and their structures solved by microcrystal diffraction using synchrotron radiation. In both cases, the SDA has been located crystallographically. The first material, [F, Cyclam]-AlPO-CHA, has the molecular formula Al-6 P6O24F2.C10N4H26 and has a framework structure related to the mineral chabazite, with the cyclam molecules occluded within chabazite-like cages (space group P-1, a = 9.0993(4), b = 9.2232(5), c = 9.3929(4) Angstrom, a = 77.881(2)degrees, beta = 87.205(1)degrees, gamma = 87.777(1)degrees, Z = 1, wR(F-2) = 0.1354, R(F) = 0.0487). The second material, [F, Cu-Cyclam]-AlPO-SAS, has the molecular formula Al8P8O32F2.[CuC10N4H24.2H(2)O] and has a framework structure closely related to STA-6 (SAS) zeolite structure type, although the usual tetragonal symmetry has been reduced to monoclinic by the presence of the fluoride ions (space group P2(1)/n, a = 10.3738(4) Angstrom, b = 14.8060(5) Angstrom, c = 13.4494(5) Angstrom, beta = 90.275(1)degrees, Z = 2, wR(F-2) = 0.1484, R(F) = 0.0524). The cyclam is occluded as a copper complex ordered within the cages of the structure. (C) 2002 Elsevier Science (USA).