Structural study of semi-coordination in a seven-coordinate copper(II) complex: distortion isomerism of [Cu(CH3COO)2(4-aminopyridine)2(H2O)]

Valach, F.; Grobelny, R.; Głowiak, Tadeusz; Mroziński, Jerzy; Lukeš, Vladimı́r; Blahová, Z.

doi:10.1080/00958972.2010.489204

Cited by 16 publications

(9 citation statements)

References 13 publications

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“…There are some interesting reports on semi-coordinated bonds found in crystal structures of Cu II cations staying within this Cu-O distance limits [29][30][31][32]. The strength of metal-ligand bonds depends on the bond length [33].…”

Section: Introductionmentioning

confidence: 97%

Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear CuII–4f Complexes with Bicompartmental Schiff Base Ligand

et al. 2019

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Classic Cu–O coordination bonds in 1 or elongated semi-coordination ones in 2 and 3 were applied to construct CuII–4f complexes composed of trinuclear subunits linked through μ-NO3− ions with formulae given as [Cu2Tm(H2tehy)2]2(NO3)6·H2O, (1), {[Cu2Ho(H2tehy)2(NO3)2][Cu2Ho(H2tehy)2(H2O)2]}(NO3)4·2H2O, (2), and {[Cu2Er(H2tehy)2(H2O)]2([Cu2Er(H2tehy)2(NO3)]2}(NO3)10·2H2O·4CH3OH, (3), where H2tehy = C19H20N2O4 is a tetrahydroxy Schiff base ligand. Topological analysis showed that the same characteristic motif of coordination accompanied by hydrogen bonds involving the uncoordinated nitrate oxygen atom and ligand’s phenoxy O atoms is responsible for linking trinuclear subunits into a hexanuclear one as well as for bridging the hexanuclear coordination units in 3 into a 1D supramolecular polymer, with the Cu–O distance being 3.19(1) Å, much longer than the limit of a semi-coordination bond (3.07 Å). The Cambridge Structural Database was used to discuss issues of crystallographic criteria (distance and angular preferences) for the assessment of the stabilizing or destabilizing effect of hydrogen bonding on coordination. The presented results show that the symmetrically repeated arrangement of molecules may provide a useful tool for identifying higher order non-covalently bonded supramolecular aggregates. The complexes 1–3 have been characterized by X-ray diffraction, FTIR, and thermal analysis. The magnetic studies indicated the ferromagnetic interaction between CuII and HoIII ions.

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Section: Introductionmentioning

confidence: 97%

Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear CuII–4f Complexes with Bicompartmental Schiff Base Ligand

et al. 2019

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“…Although the O OCO ···Cu distance of 3.014(4) Å exceeds the sum of the van der Waals radii of the atoms involved (2.92 Å), the close proximity of the metal ion to the mean plane of the square pyramid base (0.09 Å) is indicative of an attractive interaction. Complexes of similar composition, [Cu (OOCR) 2 (Py X ) 2 (H 2 O)], were reported previously by the research groups of Smith (R = ‐CH 2 O(2‐FC 6 H 4 ) and ‐CH 2 O(2‐Me,4‐ClC 6 H 3 ); X = H) and Valach (R = Me; X = NH 2 ) …”

Section: Resultsmentioning

confidence: 58%

Tweaking the affinity of aryl‐substituted diazosalicylato‐ and pyridine ligands towards Zn (II) and its neighbors in the periodic system of the elements, Cu (II) and Cd (II), and their antimicrobial activity

Baul

Nongsiej

Ka-ot

et al. 2019

Applied Organom Chemis

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A series of six new Zn (II) compounds, viz., [Zn(HLASA)2(Py)2] (1), [Zn(HLMASA)2(Py)2] (2), [Zn(HLMASA)2(4‐MePy)2] (3), [Zn(HLCASA)2(4‐MePy)2] (4), [Zn(HLBASA)2(Py)2] (5), [Zn(HLBASA)2(4‐MePy)2] (6) and representative Cu (II) and Cd (II) complexes, viz., [Cu(HLASA)2(Py)2(H2O)] (7) and [Cd(HLBASA)2(Py)3] (8) [(HLXASA)− = para‐substituted 5‐[(E)‐2‐(aryl)‐1‐diazenyl]‐2‐hydroxybenzoate with X = H (ASA), Me (MASA), Cl (CASA) or Br (BASA); Py = pyridine; 4‐MePy = 4‐methylpyridine] have been synthesized and characterized by spectroscopic techniques and single‐crystal X‐ray diffraction analysis. The structural characterization of the compounds revealed distorted tetrahedral (1–6), square‐pyramidal (7) and pentagonal‐bipyramidal (8) coordination geometries around the metal atom, in which the aryl‐substituted diazosalicylate ligands are coordinated only through the oxygen atoms of carboxylate groups, either in an anisobidentate or isobidentate mode; meanwhile, the 2‐hydroxy groups of the monoanionic ligand (HLXASA)− are involved only in intramolecular O‐H···O hydrogen bonds with the carboxylate function. In the crystal structures of 1–8, the complex molecules are assembled by π‐stacking interactions giving mostly infinite 1D strands. The intermolecular binding in the solid state structures is accomplished by diverse additional non‐covalent contacts including C‐H···O, C‐H···N, C‐H···π, C‐H···Br, O···Br, Br···π and van der Waals contacts. Although the primary and secondary ligands in the Zn (II) complex series 1–6 carry different substituents at the periphery (X = H, Me, Cl, Br for (HLXASA)− and R = H, Me for 4‐Py‐R), five of the crystal structures were isostructural. Additionally, the antimicrobial activity of the pro‐ligands H2LXASA and their Zn (II), Cu (II) and Cd (II) compounds were studied in a comparative manner, showing high sensitivity (IZD ≥ 20) against Bacillus subtilis.

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“…In both structures, Cu(II) ions are displaced from the oxygen atoms plane (0.182 Å (6); 0.212 Å ( 7)) towards the apical position. In addition, the square base angles range from 87.45° to 169.37° with a slight deviation of the square-planar geometry ( = 0.0035 (6) and = 0.0072 ( 7)) [33]. The Cu••Cu intermolecular distances are 2.6057(5) Å and 2.656(1) Å, (6 and 7, respectively).…”

Section: Crystal Structures Of Compounds Andmentioning

confidence: 97%

“…Several parameters are established to distinguish between them: the value which range from 1 (D3h) to 0 (C4v) [30], the Lapical-M-Lbasal angle (102° for C4v) or the dihedral angles between the apical faces (53.1° for D3h, 75.7° for C4v) and the apical-basal faces (101.5° for D3h, 119.8° for C4v) [31]. All these compounds clearly exhibit a C4v geometry, taking into account these three factors: All the Cu-O and Cu-N distances for the three compounds are in the same order as described in the literature [17,[32][33][34][35][36] (Table 3). For 2, Cu(II) ion is 0.109 Å displaced out of the basal plane towards the axial site while in 3 and 4a, Cu(II) ion is displaced 0.029 Å and 0.062 Å, respectively.…”

Section: Structural Studiesmentioning

confidence: 98%

“…Furthermore, the addition of the acetyl group in 4a allows the formation of supplementary interactions: one aliphatic hydrogen of the acetyl group interacts with the oxygen atom of the dioxole ring propagating the 1D chain along the c axis and forming 2D layers along the bc plane. Interestingly, there are few structures with similar 1D chain with a double H-bond interaction belonging from water -carboxylate [17,[32][33][34][35][36], which distinguishes compound 4a from the rest is the presence of three methanol and one occluded water molecules. Its supramolecular 2D squaregrid extended structure (Fig.…”

Section: Structural Studiesmentioning

confidence: 99%

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Reactivity of homoleptic and heteroleptic core paddle wheel Cu(II) compounds

Sánchez-Férez

Guerrero

Ayllón

et al. 2019

Inorganica Chimica Acta

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The compound [Cu(μ-Pip)(μ-OAc)(MeOH)]2 (1) (Pip=Piperonylate, OAc=acetate, MeOH=methanol) has been obtained in high percentage yield. Its reactivity with pyridine/pyrazole derivative ligands (pyridine (py), 3-phenylpyridine (3-Phpy) and 4-acetylpyridine (4-Acpy)) and 3,5-dimethylpyrazole (3,5-dmpz) leads to four monomeric compounds: [Cu(Pip)2(dPy)2(H2O)] (dPy=py (2), 3-Phpy (3) and 4-Acpy (4a)) and [Cu(Pip)2(3,5-dmpz)2] (5). Furthermore, the reaction of 1 with HPip in MeOH:DMF solvent under reflux conditions yields the homoleptic core paddle-wheel compound [Cu(μ-Pip)2(DMF)]2•2DMF (6). The reaction between 6 and 2-benzylpyridine (2-Bzpy) yields the paddlewheel core compound [Cu(Pip)2(2-Bzpy)]2 (7). All compounds have been fully characterized by analytical and spectroscopic techniques and their X-ray crystal structures have been determined. In this set of compounds, the carboxylate ligand (Pip) displays different coordination modes (monodentate (2-4), bidentate chelate (5) and bridged (1, 6 and 7)). Moreover, their extended structures are discussed: the crystal packing indicates hydrogen bond propagation, which defines 1D (2-5) or 2D (6 and 7) supramolecular networks...

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Structural study of semi-coordination in a seven-coordinate copper(II) complex: distortion isomerism of [Cu(CH₃COO)₂(4-aminopyridine)₂(H₂O)]

Cited by 16 publications

References 13 publications

Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear CuII–4f Complexes with Bicompartmental Schiff Base Ligand

Symmetry in Recognition of Supramolecular Synthons–Competition between Hydrogen Bonding and Coordination Bond in Multinuclear CuII–4f Complexes with Bicompartmental Schiff Base Ligand

Tweaking the affinity of aryl‐substituted diazosalicylato‐ and pyridine ligands towards Zn (II) and its neighbors in the periodic system of the elements, Cu (II) and Cd (II), and their antimicrobial activity

Reactivity of homoleptic and heteroleptic core paddle wheel Cu(II) compounds

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