Isophthalate Ligands Research Articles

Poly[diaquatris(μ4-isophthalato)dilanthanum(III)

In the title coordination polymer, [La2(C8H4O4)3(H2O)2]n, there are two independent LaIII atoms which are coordinated differently in slightly distorted penta­gonal-bipyramidal and slightly disorted bicapped trigonal-prismatic environments. The LaIII ions are bridged by μ4-isophthalate ligands, forming two-dimensional layers. In the crystal structure, these layers are connected by inter­molecular O—H⋯O hydrogen bonds into a three-dimensional network.

Dinuclear alkoxo-bridged copper(II) coordination polymers: Syntheses, structural and magnetic properties

The alkoxo-bridged dinuclear copper(II) complexes [Cu2(ap)2(NO2)2] (1), [Cu2(ap)2(C6H5COO)2] (2) and [Cu2(ap)2μ-1,3-C6H4(COO)2(dmso)2]·dmso (3) (ap = 3-aminopropanolato and dmso = dimethyl sulfoxide) have been synthesized via self-assembly from copper(II) perchlorate, 3-aminopropanol as main chelating ligand and nitrite and isophthalate anions as spacers and benzoate anion as auxiliary ligand. Complexes 1 and 3 crystallize as 2D and 1D coordination polymers, respectively, and their structures consist of dinuclear [Cu2(ap)2]2+ units connected with nitrite and isophthalate ligands. The adjacent dinuclear units of 2 and 1D polymers of 3 are further connected by hydrogen bonds resulting in the formation of 2D layers. The variable temperature crystallographic measurements of 1 at 100, 173 and 293 K indicate the static Jahn–Teller distortion with librational disorder in the nitrite group. Experimental magnetic studies showed that complexes 1–3 exhibit strong antiferromagnetic couplings. The values of the magnetic exchange coupling constant for 1–3 are well reproduced by the theoretical calculations.

Catena-Poly[[bis(μ-3-carboxybenzoato)bis(1,10-phenanthroline)tricopper(II)]-di-μ3-isophthalato

The title copper coordination polymer, [Cu3(C8H4O4)2(C8H5O4)2(C10H8N2)2]n, was synthesized by reacting Cu(NO3)2, isophthalic acid and 1,10-phenanthroline under hydro­thermal conditions. The trinuclear unit presents a central almost planar CuO4 chromophore with the cation on a symmetry center, and two symmetry-related CuN2O3 groups with the metal centre in a distorted square-pyramidal environment. These units are bridged by isophthalate ligands into one-dimensional double-chain coordination polymers which are, in turn, connected by various π–π stacking inter­actions (face-to-face distance ca 3.45 Å) and O—H⋯O hydrogen bonds, forming a three-dimensional supra­molecular network.

Catena-Poly[[bis(1-ethylimidazole-κN3)cobalt(II)]-μ-isophthalato-κ2O1:O3

In the title compound, [Co(C8H4O4)(C5H8N2)2]n, each cobalt(II) ion is coordinated by two N and two O atoms in a distorted tetra­hedral geometry. The isophthalate ligands bridge the metal ions to form polymeric zigzag chains extending along the b axis. Weak C—H⋯O inter­actions contribute to the crystal packing stability.

Catena-Poly[[aqua(1,10-phenanthroline-κ2N,N′)zinc(II)]-μ-5-[4-(hydroxymethyl)benzyloxy]isophthalato-κ3O1,O1′:O3-[aqua(1,10-phenanthroline-κ2N,N′)zinc(II)]-μ-5-[4-(hydroxymethyl)benzyloxy]isophthalato-κ2O1:O3

The title compound, [Zn(2)(C(16)H(12)O(6))(2)(C(12)H(8)N(2))(2)(H(2)O)(2)](n), consists of linear chains formed through 5-[4-(hydroxymethyl)benzyloxy]isophthalate (mabobdc) ligands linking five- and six-coordinated Zn(II) ions. The linear chains are linked into a bilayer network via O-H...O hydrogen bonds. Adjacent bilayer structures are further linked with each other via C-H...O hydrogen bonds and pi-pi and C-H...pi interactions to give a three-dimensional supramolecular framework. The results demonstrate the coordination and supramolecular chemistry of the mabobdc ligand.

An easy way to achieve three‐dimensional metal–organic coordination polymers: synthesis and crystal structure of dizinc diisophthalate bis‐dimethylsulfoxide monohydrate: [Zn2(ip)4(DMSO)2(H2O)·3 DMSO]n

AbstractAn easy way of producing three‐dimensional metal–organic coordination polymers involving zinc(II) benzene‐dicarboxylates is reported. The reaction of zinc oxide with benzene dicarboxylic acids in water yielded the expected hydrated zinc dicarboxylates. These zinc compounds were then suspended in dimethylsulfoxide and heated to above 100 °C for a couple of hours; the solutions were allowed after filtration to cool down to eventually deliver crystalline compounds displaying complex zeotype structures. The crystal structure of the title compound, [Zn2(ip)4(DMSO)2(H2O)·3 DMSO]n (ipH2 = isophthalic acid = 1,3‐benzenedicarboxylic acid, DMSO = dimethylsulfoxide), is reported for the first time and shows a three‐dimensional network where octahedrally and tetrahedrally coordinated zinc atoms (present in a 1:1 ratio) are linked by bridging isophthalate ligands. The complex coordination network exhibits a remarkable channel structure along the z‐axis. The related zinc terephthalate–DMSO complex was similarly prepared and the crystal structure determination revealed an already documented zeotypic structure: [{Zn4(OH)2(tp)3(DMSO)4} 2H2O]n (tpH2 = terephthalic acid = 1,4‐benzenedicarboxylic acid). Weak interactions as well as hydrogen bonds involving water molecules and carboxy groups play a major role in the formation of these complex three‐dimensional networks. In comparison, the zinc 1,2‐benzene‐dicarboxylate–DMSO complex could not be isolated, even under more drastic conditions. The higher symmetry of the coordination network found in the zinc terephthalate–DMSO complexes was incidentally corroborated by 13C CP/MAS spectroscopy. Copyright © 2007 John Wiley & Sons, Ltd.

Catena-Poly[[bis(benzene-1,3-dicarboxylato-κ2O,O′)zinc(II)]-μ-4,4′-bipyridine-κ2N:N′

In the title compound, [Zn(C8H5O4)2(C10H8N2)]n, the ZnII atom lies on a twofold rotation axis, and is coordinated by two N atoms of two 4,4′-bipyridine ligands and two carboxyl­ate groups, each in a chelating mode, from two isophthalate ligands. The 4,4′-bipyridine ligand, located on an inversion center, bridges the ZnII atoms, forming a one-dimensional zigzag chain structure. O—H⋯O hydrogen bonds and π–π stacking inter­actions [with a shortest atom-to-atom distance of 3.41 (1) A] are observed between the chains.

Bis(μ-3-amino-5-carboxybenzoato-κ2O:O′)bis[(5-aminoisophthalato)triaquasodium(I)

In the title dinuclear complex, [Na2(C8H6NO4)2(C8H7NO4)2(H2O)6], which is located on a crystallographic inversion centre, each Na+ cation is coordinated by three carboxylate O atoms from three isophthalate ligands and by three water mol­ecules, displaying a distorted octa­hedral geometry. The separation in the centrosymmetric dinuclear complex is 10.251 (3) A. Intra- and inter­molecular N—H⋯O and O—H⋯O hydrogen bonds and π–π inter­actions (interplanar distance of about 3.43 A) produce a supra­molecular network.

Bis(2-amino-4,6-dimethylpyrimidine-κN)bis(isophthalato-κ2O,O′)copper(II) 2-amino-4,6-dimethylpyrimidine disolvate

The title compound, [Cu(C8H5O4)2(C6H9N3)2]·2C6H9N3, is a neutral mononuclear copper(II) complex. The Cu2+ cation lies on an inversion centre, coordinated by the N atoms from two 2-amino-4,6-dimethyl­pyrimidine ligands and four O atoms from two chelating isophthalate ligands, in a distorted octa­hedral configuration. The asymmetric unit also contains a 2-amino-4,6-dimethyl­pyrimidine solvent mol­ecule. The crystal structure is stabilized by a network of O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds and π–π stacking inter­actions, forming a three-dimensional supra­molecular structure.

Blue luminescent complexes based on 5-aminodiacetic isophthalic ligand

The reactions of Cd(CH 3COO) 2·2H 2O or Zn(CH 3COO) 2·2H 2O and 5-aminodiacetic isophthalic acid (H 4adip) with 1,10′-phenanthroline (phen) ligand gave rise to two blue luminescent coordination mononuclear complexes: [Cd(phen)(H 3adip) 2(H 2O) 2]·0.5H 2O ( 1) and Zn(phen)(H 3adip) 2 ( 2), respectively. 1 crystallizes in the triclinic space group P-1, with a=6.2889(2), b=16.1556(5), c=18.4277(7) Å, α=97.722(12), β=94.338(9), γ=95.039(7)°, V=1840.86(11) Å 3, Z=2. Complex 2 crystallizes in monoclinic, space group C2/ c with a=22.639(8), b=9.813(3), c=15.708(6) Å, β=110.928(4)°, V=3259(2) Å 3, Z=4. Carboxylic groups in both structures are involved in strong hydrogen bonding interactions. At room temperature, complex 1 exhibits an intense emission at 474 nm upon 380 nm excitation, while complex 2 exhibits an intense emission at 485 nm upon 365 nm excitation, which are contributed from ligand-to-metal charge-transfer (LMCT).

Hydrogen bonding and π–π stacking in di-μ-isophthalato-bis[bis(isonicotinamide)copper(II)] trihydrate

In the title complex, [Cu2(C8H4O4)2(C6H6N2O)4]·3H2O, the CuII atom exhibits distorted trigonal–bipyramidal geometry and is coordinated by two N atoms of two isonicotinamide (inta) ligands and three O atoms of three isophthalate (ipt) ligands. C—H⋯O and N—H⋯O hydrogen bonds, as well as π–π stacking inter­actions, are observed between.

(2,2′-Bipyridine)bis(hydrogen isophthalato)zinc(II)

In the title compound, [Zn(C8H5O4)2(C10H8N2)], the ZnII ion is located on a crystallographic twofold axis, which passes through the mid-point of the C—C bond of the bpy ligand. The Zn atom is four-coordinated by two carboxyl­ate O atoms from two symmetry-related hydrogen isophthalate ligands [Zn—O = 1.972 (5) A] and two N atoms from 2,2′-bi­pyridine ligand [Zn—N = 2.067 (5) A] to furnish a distorted tetrahedral geometry.

A novel two-dimensional layer network composed of cadmium and bridging isophthalate ligand

The first isophthalate (IPT) ligand bridging cadmium two-dimensional network coordination polymer, Cd 2·(IPT) 2·(C 5H 5N) 2 ( 1), was synthesized using 1,3-dicyanobenzene. The IPT adopts a μ 5 and μ 6-bridging mode and connects with Cd to form the double-layered square grid structure.

Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X‐Ray Crystal Structures of [Mn(ph)(Phen)2(H2O)]· 4H2O, [Mn(Phen)2(H2O)2]2(Isoph)2(Phen)· 12H2O and {[Mn(Isoph)(bipy)]4· 2.75biby}n(phH2 = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10‐Phenanthroline; bipy = 2,2‐Bipyridine)

Manganese(II) acetate reacts with phthalic acid (phH2) to give [Mn(ph)]·0.5H2O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)]·2H2O (2) and [Mn(ph)(phen)2(H2O)]·4H2O (3). Reaction of isophthalic acid (isophH2) with manganese(II) acetate results in the formation of [Mn(isoph)]·2H2O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn2 (isoph)2(phen)3)]·4H2O (5), [(Mn(phen)2(H2O)2]2(isoph)2(phen)·12H2O (6) and {[Mn(isoph)(bipy)]4·2.75 biby}n (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the “metal free” 1,10-phenanthroline and its manganese complexes were found to be active.

Synthesis, crystal structure and magnetic properties of an isophthalate-bridged manganese(II) chain complex

An isophthalate-bridged manganese(II) chain complex of [Mn 2(phen) 4( m-phth)] n [ClO 4] 2 n ·2 nH 2O, where phen is 1,10- phenanthroline and m-phth is isophthalate (dianion of benzene-1,3-dicarboxylic acid), has been prepared and characterized by X-ray crystallography and magnetic measurements. It crystallizes in the triclinic system, space group P 1 ̄ , with a=14.651(1), b=16.679(7), c=13.561(4) Å, α=101.46(3), β=113.91(2), δ=65.52(3)° and Z=2. The structure consists of cationic isophthalate-bridged [Mn 2(phen) 4( m-phth)] 2+ chains, non-coordinated perchlorate anions and crystallized water molecules. Each isophthalate is bound to four manganese atoms through carboxylate oxygens with the syn–syn bridging mode, affording manganese(II) pairs which are linked by the isophthalate group to yield a one-dimensional chain running along the a axis. The intrachain Mn⋯Mn separations are 4.86 and 4.66 Å (through the double carboxylate bridges) and 7.16 Å (the shortest distance through the bridging isophthalate), respectively. The manganese(II) ion displays a distorted octahedral coordination being linked to four nitrogen atoms of two phen ligands and two oxygen atoms of two carboxylate groups from two isophthalate ligands. The variable temperature magnetic susceptibility of the title complex in the temperature range 1.5–300 K has been interpreted in terms of an Mn(II) dimer with a molecular field approximation, the values obtained for J, g(fixed) and z J′ being 3.23 cm −1, 2.00 and −0.35 cm −1, respectively, indicating a weakly ferromagnetic exchange coupling within the Mn(II) dimer with double carboxylates in syn–syn conformation.

Synthesis, crystal structure and magnetic properties of an isophthalate-bridged manganese(II) chain complex

An isophthalate-bridged manganese(II) chain complex of the formula [Mn 2(bipy) 4( m-phth)] n -[ClO 4] 2 n ·4 nH 2O, where bipy is 2,2′-bipyridine and m-phth is isophthalate (dianion of benzene-1,3-dicarboxylic acid), has been prepared and characterized by X-ray crystallography and magnetic measurements. The structure consists of cationic isophthalate-bridged [Mn 2(bipy) 4( m-phth)] 2+ chains, non-coordinated perchlorate anions and water molecules of crystallization. Each isophthalate ligand is bound to four manganese atoms through carboxylase oxygens with the syn-syn bridging mode, affording manganese(II) pairs that are linked by the isophthalate group to yield a one-dimensional chain running along the c-axis. The manganese(II) ion displays a distorted octahedral coordination being linked to four nitrogen atoms of two bipy ligands and two oxygen atoms of two carboxylate groups from two isophthalate ligands. The variable temperature magnetic susceptibility of the title complex in the temperature range 4–300 K has been interpreted in terms of Mn II dimer with a molecular field approximation, and the values obtained for J, g(fixed) and zJ′ being −0.98 cm −1, 2.00 and − 0.03 cm −1, respectively, indicating a weakly antiferromagnetic exchange coupling between the Mn II ions.