Layered tin(II) oxalates possessing large apertures

Two layered tin(II) oxalate structures have been prepared by hydrothermal m ethods in the presence of structure-directing organic amines, The crystal d ata for these structures are as follows: oxalate I, [(CH3)(2)NH(CH2)(2)NH(C H3)(2)](2+)[Sn-2(C2O4)(3)](2-). H2O, monoclinic, space group C2/c (no. 15), a = 16.567 (8) Angstrom, b = 10.851 (6) Angstrom, c 11.652 (6) Angstrom, b eta = 102,62 (3)degrees, V = 2039.0 (1) Angstrom(3), Z = 4, M = 637.4(1), D -calc = 2.825 g cm(-3), Mo K alpha, R-F = 0.04; oxalate II, [C(NH2)(3)](2)( +)[Sn-4(C2O4)(5)](2-). 2H(2)O, orthorhombic, space group Pbca (no. 61), a = 11.390 (1) Angstrom, b = 14.742 (1) Angstrom, c = 16.755 (1) Angstrom, V = 2813,1 (1) Angstrom(3), Z = 8, M = 1070.8(1), D-calc = 2.844 g cm(-3), Mo K alpha, R-F = 0.06. In I, pseudo-pentagonal-bipyramidal SnO6 units form a puckered layered structure by sharing oxygens with the oxalate anions. The layers contain 8- and 12-membered apertures, and the amine (protonated N,N, N'N'-tetramethyl-1,2-diaminoethane) and water molecules are in the interlam ellar region where they interact with the framework and with each other by hydrogen bonding. The lone pairs of the Sn(II) atoms point into the interla mellar region. Oxalate II contains both square-pyramidal SnO4 units and SnO 6 units similar to those in I. These units together form a saw-tooth lamell ar structure by linking through the oxalates. The sheets contain 20-membere d corrugated rings, which hold two amine cations (guanidinium) and two wate r molecules, which interact with the framework via hydrogen bonding.