New gallium phosphate frameworks containing 1,4-diaminobutane and 1,5-diaminopentane:: [NH3(CH2)xNH3][Ga4(PO4)4(HPO4)] and [NH3(CH2)xNH3][Ga(PO4)(HPO4)] (x=4 and 5)

Two new gallium phosphates, [NH3(CH2)(4)NH3][Ga-4(PO4)(4) (HPO4)] (I) and [NH3(CH2)(4)NH3][Ga(PO4)(HPO4)] (II), have been synthesized under solvothermal conditions in the presence of 1,4-diaminobutane and their structures determined using room-temperature single-crystal X-ray diffraction data. Compound (I) (M-r = 844.90, triclinic, space.group P-1, a = 9.3619(3), b = 10.1158(3) and c = 12.6456(5) Angstrom, alpha = 98.485(1), beta = 107.018(2) and gamma = 105.424(1)degrees; V = 1070.39 Angstrom(3), Z = 2, R = 3.68% and R-w = 4.40% for 2918 observed data [I > 3(sigma(I))]) consists of GaO4 and PO4 tetrahedra and GaO5 trigonal bipyramids linked to generate an open three-dimensional framework containing 4-, 6-, 8-, and 12-membered rings of alternating Ga- and P-based polyhedra. 1,4-Diaminobutane dications are located in channels bounded by the 12-membered rings in the two-dimensional pore network and are held to the framework by hydrogen bonding. Compound (II) (M-r = 350.84, monoclinic, space group P2(1)/c, a = 4.8922(1), b = 18.3638(6) and c = 13.7468(5) Angstrom, = 94.581 (1)degrees; V = 1227.76 Angstrom(3), Z = 4, R = 2.95% and R-w = 3.37% for 2050 observed data [I > 3(sigma(I))]) contains chains of edge-sharing 4-membered rings of alternating GaO4 and PO4 tetrahedra constituting a backbone from which hang 'pendant' PO3(OH) groups. Hydrogen bonding between the GaPO framework and the diamine dications holds the structure together. A previously reported phase, [NH3(CH2)(4)NH3][Ga-4(PO4)(4)(HPO4)] (V), structurally related but distinct from its stoichiometric equivalent, (I), has been prepared as a pure phase by this method. Two further materials, [NH3(CH2)(5)NH3][Ga-4(PO4)(4)(HPO4)] (III) (triclinic, lattice parameters from PXD: a = 9.3565(4), b = 5.0156(2) and c = 12.7065(4) Angstrom, alpha = 96.612(3), beta = 102.747(4) and gamma = 105.277(3)degrees) and [NH3(CH2)(5)NH3][Ga(PO4)(HPO4)] (IV) (M-r = 364.86, monoclinic, space group P2(1)/n, a = 4.9239(2), b = 13.2843(4) and c = 19.5339(7) Angstrom, beta = 96.858(1)degrees; V = 1268.58 Angstrom(3), Z = 4, R = 3.74% and R-w = 4.44% for 2224 observed room-temperature data [I > 3(sigma(I))]) were also prepared under similar conditions in the presence of 1,5-diamino-pentane. (III) and (IV) are structurally related to, yet distinct from (I) and (II) respectively. (C) 2002 Elsevier Science (USA).