The interplay of hydrogen-bonding and metal-coordination motifs in the formation of supramolecular patterns: Copper/zinc malonates–aminopyrimidine complexes

Hemamalini, Madhukar; Muthiah, Packianathan Thomas; Butcher, R.J.; Lynch, Daniel Ε.

doi:10.1016/j.inoche.2006.07.032

Cited by 18 publications

(12 citation statements)

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“…In contrast, in this regard, the use of carboxylic acid ligands with thiophene skeleton to construct Cu (II)– carboxylate compounds has been less investigated to date. Pyrimidine and aminopyrimidine derivatives are biologically very important compounds as they are components of nucleic acids [14]. The carboxylate group exhibits a variety of coordination behaviour displaying non identical bonding modes towards metal cations, such as monodentate and chelate, as well as η 1 :η 2 :μ 2 bridging ligands in syn, syn, syn, anti, and anti,anti conformations [15,16].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Jenniefer

Muthiah

2013

Chemistry Central Journal

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BackgroundVarious dinuclear copper (II) complexes with octahedral geometry have been reported. The majority of these complexes contain N containing aromatic rings as axial ligands. There are also a few cases where the solvent used in the reaction occupies the axial position of the dinuclear copper (II) complex. This may occur by planned synthesis or some times by serendipity. Here we report some four copper (II) complexes containing solvent and or N containing heterocyclic ring as the axial ligand.ResultsFour compounds, each containing dinuclear Copper (II) units (with the most robust, frequently occurring paddle wheel structures) were synthesized and characterised by single crystal X-ray diffraction and by IR spectroscopy. The compounds 1 & 2 have the general formula Cu2(RCOO) 4(L)2 [(for (1) RCOO= 4-Chloro Benzoate, L= Isopropanol; for 2 RCOO= Benzoate, L= 2-Amino-4,6-dimethyl pyrimidine )] while 3 & 4 have the general formula, Cu2(RCOO) 4(S)2 Cu2(RCOO) 4(L)2 [RCOO=5-Chloro-thiophene-2-carboxylate L= 2-Amino-4,6-dimethyl pyrimidine, for 3 S= ethanol; for 4 S= methanol ]. A wide range of hydrogen bonds (of the O-H…O, N-H…O and N-H…N type) and π-π stacking interactions are present in the crystal structures.ConclusionsAll compounds contain the dinuclear units, in which two Cu (II) ions are bridged by four syn, syn-η1:η1:μ carboxylates, showing a paddle-wheel cage type with a distorted octahedral geometry. The compounds 1 &2 contain a single dimeric unit while 3 &4 contain two dimeric units. The structures 3 and 4 are very interesting co-crystals of two paddle wheel molecules. Also it is interesting to note that the compounds 3 &4 are isostructural with similar cell parameters. Both the compounds 3 &4 differ in the solvent molecule coordinated to copper in one of the dimeric units. In all the four compounds, each of the copper dimers has an inversion centre. Every copper has a distorted octahedral centre, formed by four oxygen atoms (from different carboxylate) in the equatorial sites. The two axial positions are occupied by copper and the corresponding ligand.

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Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Jenniefer

Muthiah

2013

Chemistry Central Journal

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“…The ladder motif, as observed in the crystal lattice, is shown in Fig. 2(b) (Hemamalini et al, 2006;Prabakaran et al, 2000;Jenniefer & Muthiah, 2014). Another supramolecular ladder is formed by two R 4 4 (16) ring motifs involving O5-H5BÁ Á ÁO6, O6-H6BÁ Á ÁCl1 iv and O6-H6AÁ Á ÁO2 iii hydrogen bonds, made up of metal ions, carboxylate groups, chloride ions and both types (coordinated and uncoordinated) of water molecules.…”

Section: Tablementioning

confidence: 79%

“…The discrete coordination/ coordination polymers/MOFs further self-assemble via a variety of noncovalent interactions, generating supramolecular architectures (Cook et al, 2013;Amo-Ochoa & Zamora, 2014). Several mixed-ligand complexes and supramolecular architectures have already been reported by our groups (Hemamalini et al, 2006;Jenniefer & Muthiah, 2013;Jenniefer & Muthiah, 2014;Perdih, 2012;Koleša-Dobravc et al, 2015). In this work, two well studied and versatile ligands, viz.…”

Section: Introductionmentioning

confidence: 80%

Supramolecular architectures in Co^IIand Cu^IIcomplexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands

2016

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The coordination chemistry of mixed-ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal-organic framworks are emerging as novel functional materials. Aminopyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic-inorganic hybrid materials and coordination polymers. Thiophenecarboxylic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thiophenecarboxylate have many biological applications, for example, as antifungal and antitumor agents. Two new cobalt(II) and copper(II) complexes incorporating thiophene-2-carboxylate (2-TPC) and 2-amino-4,6-dimethoxypyrimidine (OMP) ligands have been synthesized and characterized by X-ray diffraction studies, namely (2-amino-4,6-dimethoxypyrimidine-κN)aquachlorido(thiophene-2-carboxylato-κO)cobalt(II) monohydrate, [Co(C5H3O2S)Cl(C6H9N3O2)(H2O)]·H2O, (I), and catena-poly[copper(II)-tetrakis(μ-thiophene-2-carboxylato-κ(2)O:O')-copper(II)-(μ-2-amino-4,6-dimethoxypyrimidine-κ(2)N(1):N(3))], [Cu2(C5H3O2S)4(C6H9N3O2)]n, (II). In (I), the Co(II) ion has a distorted tetrahedral coordination environment involving one O atom from a monodentate 2-TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water molecule. An additional water molecule is present in the asymmetric unit. The amino group of the coordinated OMP molecule and the coordinated carboxylate O atom of the 2-TPC ligand form an interligand N-H...O hydrogen bond, generating an S(6) ring motif. The pyrimidine molecules also form a base pair [R2(2)(8) motif] via a pair of N-H...N hydrogen bonds. These interactions, together with O-H...O and O-H...Cl hydrogen bonds and π-π stacking interactions, generate a three-dimensional supramolecular architecture. The one-dimensional coordination polymer (II) contains the classical paddle-wheel [Cu2(CH3COO)4(H2O)2] unit, where each carboxylate group of four 2-TPC ligands bridges two square-pyramidally coordinated Cu(II) ions and the apically coordinated OMP ligands bridge the dinuclear copper units. Each dinuclear copper unit has a crystallographic inversion centre, whereas the bridging OMP ligand has crystallographic twofold symmetry. The one-dimensional polymeric chains self-assemble via N-H...O, π-π and C-H...π interactions, generating a three-dimensional supramolecular architecture.

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“…Moreover, amino-pyrimidine derivatives are supposed to be biologically important compounds because they occur in nature as components of nucleic acids. 15 Indeed, some amino-pyrimidine compounds have been shown to have potential to act as antifolate drugs. 16 Compound 1 is the unique combination, in which both individual components are potential candidates for drug activity.…”

Section: Resultsmentioning

confidence: 99%

Non-covalent O···O interactions among isopolyanions using a cis-{MoO2} moiety by the assistance of N-H···O hydrogen bonds

2008

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An inorganic-organic hybrid material, [2-AmpH] 4 [Mo 8 O 26 ](1) has been isolated by the reaction of Na 2 MoO 4 ·2H 2 O with 2-aminopyrimidine (2-Amp) from an acidic aqueous medium. In this low pH synthesis, the organic molecule (2-Amp) gets mono-protonated (2-AmpH + ) and acts as the cation in stabilizing the octamolybdate anion in 1. Compound 1 crystallizes in the triclinic space group P-1 with a = 9⋅925 (3) (4), β = 64⋅907(4), γ = 89⋅506(4)°, Z = 1. An interesting three-dimensional supramolecular structure, having well-defined channels, is formed through N-H⋅⋅⋅O and C-H⋅⋅⋅O hydrogen bonds, in which the protonated organic cation plays a significant role. The crystal structure also reveals an unusual cluster-cluster (non-covalent O⋅⋅⋅O) interaction using cis-(MoO 2 } moieties of the isopolyanion. N-H⋅⋅⋅O hydrogen bonds, originated from pyridimidinium cation and isopolyanion, are found to influence to attain such non-covalent O⋅⋅⋅O interactions among polyoxometalate anions. An interesting helical arrangement, formed from isopolyanion and organic cation, is observed.

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The interplay of hydrogen-bonding and metal-coordination motifs in the formation of supramolecular patterns: Copper/zinc malonates–aminopyrimidine complexes

Cited by 18 publications

References 18 publications

Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Supramolecular architectures in Co^IIand Cu^IIcomplexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands

Non-covalent O···O interactions among isopolyanions using a cis-{MoO2} moiety by the assistance of N-H···O hydrogen bonds

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The interplay of hydrogen-bonding and metal-coordination motifs in the formation of supramolecular patterns: Copper/zinc malonates–aminopyrimidine complexes

Cited by 18 publications

References 18 publications

Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Synthesis, characterization and X-ray structural studies of four copper (II) complexes containing dinuclear paddle wheel structures

Supramolecular architectures in CoIIand CuIIcomplexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands

Non-covalent O···O interactions among isopolyanions using a cis-{MoO2} moiety by the assistance of N-H···O hydrogen bonds

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Supramolecular architectures in Co^IIand Cu^IIcomplexes with thiophene-2-carboxylate and 2-amino-4,6-dimethoxypyrimidine ligands