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

Abstract

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 P21/c, with lattice constants: a = 13.939(3) A, b = 8.2600(17) A, c = 13.176(3) A, β = 94.83(3)°, V = 1511.7(6) A3, Z = 4, D c = 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°) form a chain in the [010] direction. The intermolecular hydrogen bond C–H···O (C···O = 3.432(10) A, C–H···O = 151°) leads to a [010] double-chain through each unit cell. The intermolecular hydrogen bond C–H···O (C···O = 3.359(10) A, C–H···O = 173°) 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 P21/c, with lattice constants: a = 14.091(2) A, b = 10.024(2) A, c = 13.806(2) A, β = 112.41(2)°, V = 1802.8(6) A3, 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) A, N–H···O = 155° C···O = 3.364(6) A, C–H···O = 153°) generate a [010] chain. The intermolecular hydrogen bond N–H···O (N···O = 2.989(6) A, N–H···O = 128°) forms a [010] double-chain through each unit cell. The π···π stacking interation involving the pyridyl groups makes the [010] double-chain pack along the c axis to lead to a two-dimensional network.