OXYFLUORINATED COMPOUNDS WITH AN OPEN FRAMEWORK XX - SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF AZA-CROWN ETHER TEMPLATED GA5F2(HPO4)(2)(PO4)(4),C12H27N6 (MIL-1)

A new monoclinic [space group: C2/m (no. 12)] fluorinated gallium phos phate Ga5F2( HPO4)(2)(PO4)(4),C12H27N6, a = 8.6552(6) Angstrom, b = 16 .4521 (14) Angstrom, c = 11.9391 (8) Angstrom, beta = 102.993(7)degree s, V = 1656.6(2) Angstrom(3), Z = 2, has been hydrothermally synthesiz ed (180 degrees C, 24 h, autogenous pressure), in the presence of an a za-crown ether, hexacyclen trisulfate, C12H30N66+,3SO(4)(2-) (1,4,7,10 ,13,16-hexaazacyclooctadecane = A(6)18-Crown-6), as a structural agent . It exhibits an open-framework structure which consists of layers bui lt up from the corner sharing of GaO4, GaO4F, GaO4F2 and PO4 polyhedra , the layers being linked together by HPO4 groups in order to form a t hree-dimensional network, with 12-ring channels along the [100] direct ion and 8-ring channels along the [001] direction. The A(6)18-Crown-6 molecule, delocalized on two positions, is located in the larger chann els. P-31 MAS NMR spectrometry indicated a statistical site distributi on for the interlayer HPO4 groups. (C) 1998 Elsevier Science B.V.