Syntheses and crystal structures of an organometallic thiosemicarbazone and an organometallic enehydrazide

摘要

Reactions of ferrocenoylacetone with thiosemicarbazide and isonicotinic acid hydrazide generate an organometallic thiosemicarbazone 1 and enehydrazide 2, respectively. The complexes 1 and 2, which can be formulated as [C5H5FeC5H4C(O)CH2C(=NNHCSNH2)CH3] and [C5H5FeC5H4C(O)CH=C(NHNHCOC5H4N-4)CH3], have been characterized by elemental analyses, IR, NMR, UV and were structurally characterized by single-crystal X-ray crystallography. Complex 1 (C15H17FeN3OS) crystallizes in the monoclinic space group P2(1)/c, with lattice constants: a = 13.939(3) angstrom, b = 8.2600(17) angstrom, c = 13.176(3) angstrom, = 94.83(3)degrees, V = 1511.7(6) angstrom(3), Z = 4, Dc = 1.508 g cm(-3), F,(000) = 712, R-1 = 0.0602, wR(2) = 0.1526. Two intermolecular hydrogen bonds N-H... S (N... S = 3.356(8) and 3.499(7) A, N-H... S = 168 and 170 degrees) form a chain in the [010] direction. The intermolecular hydrogen bond C-H...O (C...O = 3.432(10) angstrom, C-H...O = 151 degrees) leads to a [010] double-chain through each unit cell. The intermolecular hydrogen bond C-H...O (C...O = 3.359(10) angstrom, C-H...O = 173 degrees) makes the [010] double-chain pack along the c axis to result in a two-dimensional network. Complex 2 (C20H19FeN3O2) crystallizes in the monoclinic space group P2(1)/c, with lattice constants: a = 14.091(2) angstrom, b = 10.024(2) angstrom, c = 13.806(2) angstrom, = 112.41(2)degrees, V = 1802.8(6) angstrom(3), Z = 4, D-c = 1.434 g cm(-3), F(000) = 808, R-1 = 0.0576, wR(2) = 0.1593. The strong intramolecular hydrogen bond N-H...O from the enamine N atom and carbonyl O atom stabilizes the enehydrazide. The intermolecular hydrogen bonds N-H...O and C-H....O (N...O = 2.906(6) angstrom, N-H...O = 155 degrees C...O = 3.364(6) angstrom, C-H...O = 153 degrees) generate a [010] chain. The intermolecular hydrogen bond N-H...O (N...O = 2.989(6) angstrom, N-H...O = 128 degrees) forms a [010] double-chain through each unit cell. The pi...pi stacking interation involving the pyridyl groups makes the [010] double -chain pack along the c axis to lead to a two-dimensional network.