Inclusion Compounds of Thiourea and Peralkylated Ammonium Salts. VI. Hydrogen-Bonded Host Lattices Constructed From Thiourea and Anions of Oxalic Acid and Fumaric Acid

Abstract

New inclusion complexes tetra-n-butylammonium hydrogen oxalate–thiourea (1/2), (n-C4H9)4N+.HC2O4 −.2[(NH2)2CS] (1), tetramethylammonium hydrogen fumarate–thiourea (1/1), (CH3)4N+.HC4H2O4 −.(NH2)2CS (2), di(tetraethylammonium) fumarate–thiourea (1/2), [(C2H5)4N+]2.C4H2O4 2−.2[(NH2)2CS] (3) and tetra-n-propylammonium hydrogen fumarate–thiourea–water (1/1/2), (n-C3H7)4N+.HC4H2 O4 −.(NH2)2CS.2H2O (4) have been prepared and characterized by X-ray crystallography. Crystal data, Mo Kα radiation: (1), space group P21/n, a = 8.854 (6), b = 9.992 (3), c = 32.04 (2) Å, β = 97.34 (3), Z = 4, R F = 0.055 for 2261 observed data; (2), space group P\overline 1, a = 6.269 (2), b = 8.118 (4), c = 14.562 (8) Å, α = 104.79 (4), β= 91.72 (4), γ = 101.30 (4)°, Z = 2, R F = 0.078 for 1543 observed data; (3), space group P21/n, a = 11.340 (2), b = 9.293 (6), c = 14.619 (2) Å, β = 102.41 (2)°, Z = 2, R F = 0.050 for 1856 observed data; (4), space group P2/n, a = 16.866 (4), b = 8.311  (1), c = 17.603 (2) Å, β = 104.94 (1)°, Z = 4, R F = 0.048 for 2785 observed data. In the crystal structure of (1) the tetra-n-butylammonium ions are sandwiched between puckered layers, which are constructed from thiourea-hydrogen oxalate ribbons. In the crystal structure of (2), zigzag O--H...O and C--H...O hydrogen-bonded hydrogen fumarate ribbons are linked by thiourea dimers to form a wide puckered ribbon and the crystal structure is built of a packing of these thiourea–anion composite ribbons and the cationic columns. In the layer-type crystal structure of (3) a series of thiourea–fumarate layers match the (002) planes and the (C2H5)4N+ cations occupy the intervening space. In the crystal structure of (4) the thiourea, hydrogen fumarate ions and water molecules are connected by hydrogen bonds to form wide puckered ribbons, which are crosslinked to generate a three-dimensional host framework containing open channels aligned parallel to the a axis, with the tetra-n-propylammonium cations accommodated in a single column within each channel.