OXYFLUORINATED MICROPOROUS COMPOUNDS .7. SYNTHESIS AND CRYSTAL-STRUCTURE AND ULM-5, A NEW FLUORINATED GALLOPHOSPHATE GA16(PO4)14(HPO4)2(OH)2F7, [H3N(CH2)6NH3]4,6-H2O WITH 16-MEMBERED RINGS AND BOTH BONDING AND ENCAPSULATED F-

Hitherto unknown Ga16(PO4)14(HPO4)2(OH)2F7, [H3N(CH2)6 NH3]4, 6 H2O was obtained by hydrothermal synthesis (453 K, 24 hr, autogeneous pressure) from a mixture of Ga2O3, P2O5, HF, 1,6-diaminohexane, and H2O in the ratio 1: 1: 2: 1: 80. It is orthorhombic (space group P22(1)2(1) (No. 18)) with a = 10.252(2) angstrom, b = 18.409(4) angstrom, c = 24.639(7) angstrom, V = 4649.8(9) angstrom3, Z = 4. The three-dimensional network is built up from three types of basic building units; the first, close to that already encountered for ULM-3 and -4, consists of corner-linked [Ga3(PO4)2(HPO4)F2] hexameric units composed of two PO4 tetrahdra, one HPO4 tetrahedron, two GaO4F trigonal bipyramids, and one GaO4F2 octahedron, with fluorine atoms shared between the gallium polyhedra; the second is very similar to the first except that one of the trigonal bipyramids is replaced by a tetrahedron GaO3(OH); the third is octameric Ga4(PO4)4 and can be considered in a first approximation as formed by a cube of corner-linked GaO4 and PO4 tetrahedra, which encapsulate a fluorine atom. It is shown that this fluorine is bonded in fact to two of the four gallium of this cube. For the first time, both bonding and encapsulated F- are present in the same structure. The framework delimits 16- and 6-membered ring channels along [100] and 8-membered ones along [010]. The diprotonated amines are inserted in the 16-membered ovoid channels, whose free aperture is 12.20 x 8.34 angstrom. The water molecules are in the 6-membered tunnels. (C) 1994 Academic Press, Inc.