Synthesis, Structure and Electrochemistry of Macrocyclic 1,1'-Bis(1,3-phenyleneoxyacetylpyrazoyl)ferrocene

1,1'-Diacetoacetylferrocene 1 reacted with phenylene-1,3-dioxyactyl hydrazine 2 in absolute ethanol to give the macrocyclic ferrocenyl dipyrazole compound in moderate yield. Determined by X-ray structure analysis, it crystallizes in monoclinic system, space group P21/c with a = 13.7509(4), b = 8.1277(2), c = 21.7472(6) , β = 103.1030(10)°, V = 2367.25(11) 3, Z = 4, Dc = 1.505 g/cm3, R = 0.0353 and wR = 0.0811. The electrochemical studies reveal that redox of Fe+/Fe in ferrocene is a reversible one-electron process.     

Crystal Structure of Hydrochlorate of 1,1＇-Bis[（4-pyridylamino）carbonyl]ferrocene

The hydrochlorate of 1,1?-bis[(4-pyridylamino)carbonyl]ferrocene (C23H23O3N4ClFe, Mr = 494.75) was structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in triclinic, space group P1 with a = 9.5299(19), b = 12.792(3), c = 9.2644(19) ?, α = 91.56(3), β = 101.97(3), γ = 74.71(3)°, V = 1065.2(4) ?3, Z = 2, Dc = 1.542 g/cm3, F(000) = 512, μ(MoKα) = 0.868 mm-1, T = 291(2) K, the final R = 0.0596 and wR = 0.1531 for 2842 observed reflections with I > 2σ(I). Interestingly, two 1,1?- bis[(4-pyridylamino)carbonyl]ferrocenes (4-BPFA) join shoulder-to-shoulder through intermolecular hydrogen bonds N–H…N, forming an unexpected macrocycle with dimensions of 3.385 ? × 15.778 ?.     

Polymeric methylenebis(diphenylphosphine oxide) hydrogen triiodide

The conformation of the cationic part of the title compound, [{(C₆H₅)₂POH_0.5}₂CH₂]I₃ or dppmO₂H⁺·I₃^? (dppm is di­phenyl­phosphino­methane), is determined by hydrogen bonds between cations of monoprotonated [(C₆H₅)₂P(=O)]₂CH₂ (dppmO₂). Symmetric P=O?H?O=P bridging, with H atoms lying on centres of inversion, leads to chain‐like polymeric cations, (dppmO₂H⁺)_x, made up of H?OP(C₆H₅)₂—CH₂—(C₆H₅)₂PO? moieties. These are, in turn, cross‐connected by non‐classical C—H?I contacts between the (dppmO₂H⁺)_x methyl­ene‐group H atoms and the terminal I atoms of the triiodide anions, which display crystallographic inversion symmetry.