Intermolecular O—H...O and C—H...π(C₅H₅), and intramolecular C—H...O interactions in 2-(ferrocenyl)thiophene-3-carboxylic acid

Abstract

The title compound, [Fe(C 5 H 5 )(C 10 H 7 O 2 S)], an important precursor en route to organometallic donor±%±acceptor systems, forms dimers in the solid state through cyclic intermolecular carboxylic acid OÐHÁ Á ÁO hydrogen bonds, graph set R CommentThe design of new redox-active compounds for application in materials science has engaged chemists in recent years. Ferrocene derivatives which are ef®cient redox systems have been studied extensively as charge-transfer complexes, in molecular recognition science, in peptide chemistry and as non-linear optical materials (Moore et al., 1993;Chesney et al., 1998;Glidewell et al., 1997;Kraatz et al., 1999;Hudson et al., 2001). An understanding of the interactions present in the crystal structure of a new material can provide valuable information on the hydrogen-bonding modes, thus facilitating an understanding of solid-state effects and the subsequent design and improvement of currently available systems. The structure of 2-(ferrocenyl)thiophene-3-carboxylic acid, (V), an important precursor en route to organometallic donor±%± acceptor systems, is reported herein.The synthesis of compound (V) is detailed in the Experimental section and the molecular structure is depicted, with the atomic numbering scheme, in Fig. 1; selected geometric dimensions are given in Table 1. Bond lengths are in accord with the anticipated values (Orpen et al., 1994). The unsubstituted cyclopentadienyl (Cp) ring is disordered over two sites, with occupancies of 0.691 (18) and 0.309 (18) for the major and minor orientations, respectively. Rotational disorder is often observed in the unsubstituted C 5 H 5 ring of ferrocene derivatives, e.g. 1-ferrocenyl-1-phenylethanol (Ferguson et al., 1993). The Fe1ÐC bond lengths for the substituted Cp ring of (V) are in the range 2.028 (2)± 2.050 (2) A Ê , which is similar to that observed for the major orientation of the unsubstituted Cp ring [2.039 (4)± 2.051 (7) A Ê ]. The Fe1Á Á ÁCg1 and Fe1Á Á ÁCg2 distances are 1.6435 (10) and 1.656 (3) A Ê , respectively, and the Acta Crystallographica Section C Crystal Structure CommunicationsISSN 0108-2701 Figure 1 An ORTEX (McArdle, 1995) view of (V) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The minor Cp-ring disorder form has been omitted for clarity.

Three Cu(II) Complexes Based on Mixed Ligands: Their Structures and Catalytic Behaviour

“…Similar hydrogen-bonding and C-H•••π interactions are found in reported papers. 23,24 By comparison with other metal centres, such as d 10 ions, the Cu(II) centre has fewer such interactions incorporated in the complex under the organic anion system. Su and co-workers reported two interpenetrating and one noninterpenetrating Cu(II) complexes based on the btx synthon with polyoxometalate as counter anion, which also indicates that the anion can greatly affect the final architecture, especially for polycarboxylate or polyoxometalate as anion.…”

Solvatomorphism in a series of copper(II) complexes with the 5-phenylimidazole/perchlorate system as ligands

“…Inspection of the solvatomorphs shows that the solvent molecules are situated in channels (Gallagher & Mocilac, 2021) within their crystal structures. Based on PLATON 3.2.5.…”

“…For example, for some active pharmaceutical ingredients (APIs) solvatomorphs could be the ultimate pharmaceutical form for clinical use because of their advantages in improving the solubility or stability of APIs and, therefore, the performance of the drug (Yuan et al, 2020); in biological systems where a modification of the protein solvent environment by denaturation results in changes in their biological activities; in the self-assembly of MOFs (Ko ¨ppen et al, 2018;Seetharaj et al, 2019); in organic and inorganic functional nanomaterials (Yamada et al, 2006;Bernard et al, 2018) etc. However, solvate/hydrate formation is a rather unpredictable process, as we are not able to tell in advance whether a solvent or a water molecule will crystallize with the solute molecule (Juarez-Garrido et al, 2022;Glasser, 2019;Li & Du, 2011).…”