Crystal and molecular structures of 3-acetyl-5-[2-(3-ethyl-2-benzothiazolidene)]ethylidenerhodanine and its lithium and sodium salts. Layered organic-inorganic structures

An x-ray diffraction study of the crystals of 5-[2-(3-ethyl-2-benzothiazolidine)]ethylidinerhodanine N-aceric acid (1, solvate with dimethylsulfoxide), lithium 5-[2-(3-ethyl-2-benzothiazolidine)]ethylidinerhodanine N-acetate (2, solvate with water and dimethylformamide) and sodium 5-[2-(3-ethyl-2-benzothiazolidine)]ethylidinerhodanine N-acetate (3, octahydrate) have been carried out at 295K. Crystal data for (1): C16H14N2O3S3.C2H6OS, M(r)=456.6, triclinic, a=7.664(6), b=9.874(8), c=14.851(8)Angstrom(3), space group P1, Z=2, F(000)=476, D-x-1.412g cm(-3), mu(MoK-alpha)-0.469mm(-1), R=0.0698 for 1688 reflections with F>6-sigma(F); for (2): Li+.C16H13N2O3-.2H(2O).1.5C(3)H(7)NO, M(r)=544.6, monoclinic, a=7.249(5), b=10.773(6), c=16.433(13)Angstrom, alpha equals 87.66(6), beta equals 85.22(6), gamma equals 77.04(6)degrees, V=1246(1)Angstrom(3), space group P1, Z=2, F(000)=556, D-x=1.413g cm(-3), mu(MoK-alpha)-0.342mm(-1), R=0.0551 for 2360 reflections with F>6-sigma(F); for (3) Na+.C16H13N2O3S3-.8H(2)O, M(r)=544.6, monoclinic, a=46.209(12), b=7.005(3), c=16.583(8)Angstrom, beta equals 109.45(4)degrees, V=5061(1)Angstrom(3), space group C2/c, Z=8, F(000)=2288, D-x=1.429mg m(-3), mu(MoK-alpha)-0.365mm(-1), R=0.0440 for 2680 reflections with F>6-sigma(F). Crystals (1) 1nd (2) are built up of stacks of head-to-tail oriented molecules and anions, respectively, which have alternating interplanar separations of 3.41(1) and 3.46(1)Angstrom for (1), and 3.38(1) and 3.45(1)Angstrom for (2) (so-alled H aggregation of dye). The Li+ cations and solvent molecules form the cationic layers in crystal (2), alternating withthe anionic layers along the c direction. The shifted head-t-head oriented anions in crystal (3) form uniform stacks along the b axis at the interplanar separation of 3.39(1)Angstrom (so-called J aggregation of dye). The stacks are arranged in bilayers with the O atoms on the outer surfaces of the bilayers. The inorganic layers situated between the anionic organic bilayers consist of extended chains of distorted edge-shared polyhedra of Na+ cations and water molecules. The O atoms on the outer surfaces of the bilayers do not participate in the direct ionic interactions with the Na+ cations. The structure and stability of layered organic-inorganic structures with internal surfaces are discussed by means of the crystal structures of (1)-(3) and literature data.