SYNTHESIS AND CRYSTAL-STRUCTURE OF A NEW VIV/VV MIXED-VALENCE MICROPOROUS COMPOUND V3P2O13(H2O)2, H3N(CH2)3NH3

Hitherto unknown vanado(IV, V)phosphate, ideally V(IV)V2(V)P2O13 (H2O)2, H3N(CH2)3NH3 was obtained by hydrothermal synthesis (453 K, 24 hr, autogeneous pressure) from a mixture of V2O5, P2O5, 1,3-diaminopropane, and H2O in the ratio 1:1:1.3:1:80. It is orthorhombic (space group Pnma (No. 62)) with a = 10. 567(1) angstrom, b = 16.970(2) angstrom, c = 8.413(1) angstrom, V = 1508.1(7) angstrom3, Z = 4. The three-dimensional network is built up from the corner linkage of pentameric secondary building units based on two PO4 tetrahedra, one VO5 square pyramid, and two VO5(H2O) octahedra sharing vertices. The framework delimits large 10-membered ovoid zigzag tunnels along [100] and smaller eight-membered ones along [010]. The true composition of the solid is discussed. The diprotonated amines are inserted in the 10-membered ovoid channels, whose free aperture is 7.30 x 4.00 angstrom. (C) 1994 Academic Press, Inc.