Ferrocene-1,1′-dicarboxylic acid as a building block in supramolecular chemistry: supramolecular structures in one, two and three dimensions

Abstract

The supramolecular structures have been determined for nine adducts formed between organic diamines and ferrocene-1,1'-dicarboxylic acid. In the salt-like 1:1 adduct (1) formed with methylamine, the supramolecular structure is one-dimensional, whereas in the 1:1 adducts formed with 1,4-diazabicyclo[2.2.2]octane, (2), and 4,4'-bipyridyl, (4), and in the hydrated 2:1 adduct (3) formed with morpholine, the hard hydrogen bonds form one-dimensional structures, which are expanded to two dimensions by soft C-H...O hydrogen bonds. The hard hydrogen bonds generate two-dimensional structures in the 2:1 adduct (5) formed with octylamine, where the ferrocene component lies across a centre of inversion, in the 1:1 adduct (6) formed with piperidine and in the tetrahydrofuran-solvated 1:1 adduct (7) formed with di(cyclohexyl)amine. In the 2:3 adduct (8) formed by tris-(2-aminoethyl)amine, and in the 2:1 adduct (9) formed with 2-(4'-hydroxyphenyl)ethylamine (tyramine), where Z' = 1.5 in space group P-1, the hard hydrogen bonds generate three-dimensional structures. No H transfer from O to N occurs in (4) and only partial transfer of H occurs in (2); in (1), (6) and (7), one H is transferred to N from each acid molecule, and in (3), (5), (8) and (9), two H are transferred from each acid molecule.

Mechanochemical preparation of molecular and supramolecular organometallic materials and coordination networks

“…It has been observed in hydrogen bonded adducts with bis-amidines 153 and with other bis-amines, such as 1,4-diazabicyclo[2.2.2]octane, C 6 H 12 N 2 , DABCO. 146,154 In all these cases, however, the geometry of the base did not allow cyclization and forced the system to chain formation, while the conformational freedom of [Fe(g 5 -C 5 H 4 -1-C 5 H 4 N) 2 ] permits, in principle, both linear chains and rings.…”

Synthesis, Structure, and Supramolecular Architecture of Benzonitrile and Pyridine Adducts of Bis(pentafluorophenyl)zinc: Pentafluorophenyl–Aryl Interactions versus Homoaromatic Pairing

“…In particular, supramolecular coordination complexes of zinc have received considerable attention, and examples have been considered for applications in nonlinear optics and as gas storage materials. , While dative bonding continues to dominate supramolecular coordination chemistry, there is now increasing recognition of the role that secondary interactions, such as hydrogen bonding and aryl−aryl pairing, play in determining the three-dimensional assembly of metal complexes . These are the supramolecular synthons familiar to the organic crystal engineer. – , We and others are endeavoring to direct the supramolecular assembly of organometallic complexes using the tools of organic crystal engineering and without recourse to dative bonds. – Despite the challenges associated with depending upon such weak interactions, this approach promises materials more readily processed than metal organic frameworks and with properties more closely related to discrete molecules than coordination polymers.…”

“…1a-c,6 We and others are endeavoring to direct the supramolecular assembly of organometallic complexes using the tools of organic crystal engineering and without recourse to dative bonds. [7][8][9][10][11][12][13][14] Despite the challenges associated with depending upon such weak interactions, this approach promises materials more readily processed than metal organic frameworks and with properties more closely related to discrete molecules than coordination polymers.…”

The sulfonate group as a ligand: a fine balance between hydrogen bonding and metal ion coordination in uranyl ion complexes

“…Solvothermal synthesis 50 has of course been a highly successful pathway to an enormous variety of crystalline complexes, but it is worth noting that the very numerous instances where it does not provide a crystalline product are usually not reported and that it is solubility and not necessarily solution stability that determines the nature of any isolated species. Given as well that so little is known in general of the solution equilibria existing in in most NiN4O2 species considered to involve 6-coordinate Ni II , where carboxylate-O donors, for example, 51 give Ni-O ~2.1 Å. In fact, analysis of the Hirshfeld surface (HS) 52 of the cation, calculated using CrystalExplorer (Version 3.1) 53 and shown in Fig.…”