Open-framework zinc phosphates synthesized in the presence of structure-directing organic amines

Four open-framework zinc phosphates have been synthesized in the presence o f structure-directing organic amines. Crystal data: compound I, [NH3(CH2)(2 )NH3. Zn-2(HPO4)(2)(H2PO4)(2)], monoclinic, space group=P2(1)/c (No. 14), a =16.420(2) Angstrom, b = 7.826(1) Angstrom, c = 14.640(1) Angstrom, beta = 116.47(1)degrees V= 1684.05(2) Angstrom(3), Z= 4, M = 578.8(1), D-calc = 2. 22 g cm(-3), MoK alpha, R-F = 0.05; compound II, [NH3(CH2)(2)NH3. Zn(HPO4)( 2)] monoclinic, space group=P2(1)/c (No. 14), a=5.161(1) Angstrom, b = 15.8 42(2) Angstrom, c = 12.027(2) Angstrom, beta = 92.36(2)degrees, V= 982.41(1 ) Angstrom(3), Z= 4, M= 319.45(1), D-calc = 2.16 gcm(-3), MoK alpha, R-F = 0.06; compound III, [NH3CH2CH(OH)CH2NH3. Zn-2(HPO4)(3)], monoclinic, space group=P2(1)/c (No. 14), a = 8.615(1) Angstrom, b = 9.648(1) Angstrom, c = 1 7.209(1) Angstrom, beta= 93.02(1)degrees, V= 1428.4(2), Z= 4, M = 510.8(1), D-calc = 1.79 g cm(-3), MoK alpha, R-F = 0.03; compound IV, [NH3(CH2)(6)NH 3. Zn-3(HPO4)(4)H2O], monoclinic, space group=C2/c (No. 15), a=16.815(1) An gstrom, b = 8.970(1) Angstrom, c = 15.080(1) Angstrom, beta = 97.25(1)degre es, V= 2256.4(1), Z= 4, M= 734.3(1), D-calc = 2.16 g cm(-3), MoK alpha, R-F = 0.05. The compounds are made up of ZnO4 and PO4 tetrahedra that share ve rtices. The connectivity between the ZnO4 and PO4 units gives rise to layer s in I, III, and IV and a chain architecture in II. The structure-directing organic amine holds the chains and the layers in position through multi-po int hydrogen bonding. The layers in I and III consist of bifurcated 12-memb ered rings, and those in IV, of 8-membered rings. The phosphate units occur either as hydrogen phosphate (HPO4) or dihydrogen phosphate (H2PO4) moieti es. These and other novel features in these materials suggest that further exploration may lead to many new solids with interesting structures. As a g uide to understanding the formation of different ring structures in Zn phos phates and allied materials, a possible pathway involving the basic 4-membe red ring is suggested, (C) 1999 Academic Press.