New lead triphosphonates: synthesis, properties and crystal structures

Two new lead nitrilotris (methylene) triphosphonates, Pb[(H2O3PCH2)N (CH2PO3H)(2)] I and Pb-2[(O3PCH2)N(CH2PO3H)(2)]. H2O II, have been synthesised. I is triclinic, space group <P(1)over bar>, a = 8.5077(2), b = 11.2363(3), c = 5.9484(2) Angstrom, alpha = 98.802(2), Angstrom, beta = 104.955(1), gamma = 80.911(2)degrees, Z = 2. II is monoclinic, space group Pn, a = 7.3614(2), b = 11.3889(2), c = 7.2541(2) Angstrom, beta = 100.389(2)degrees and Z = 2. Their structures have been solved from laboratory X-ray data by using ab initio powder diffraction methodology. The reliability factors were R-wP = 9.28%, R-P = 7.20% and R-F = 2.67%, for I, and R-wP = 12.51%, R-P = 9.38% and R-F = 4.45%, for II. I shows a new layered structure which has small cavities, inside an inorganic layer, in which the hydrogen phosphonate and the dihydrogen phosphonate groups are located. II is also layered with the water molecule situated in the interlamellar space. Thermal data, IR data and ion-exchange properties are also reported and discussed. II dehydrates to yield orthorhombic Pb-2[(O3PCH2)N(CH2PO3H)(2)] III. Hydrolysis of I leads to II.