Synthesis and crystal structure of a cadmium(II) coordination polymer based on 4,4'-(1-1,2,4-triazole-3,5-di-yl)dibenzoate.

The asymmetric unit of the title compound, -poly[[[aqua-bis-(pyridine-κ)cadmium(II)]-μ-4,4'-(1-1,2,4-triazole-3,5-di-yl)dibenzoato-κ ,':'','''] 4.5-hydrate], {[Cd(CHNO)(CHN)(HO)]·4.5HO} or {[Cd(bct)(py)(HO)]·4.

Crystal structures of the complexes containing macrocyclic cations [(cyclam)] ( = Ni, Zn) and tetra-iodido-cadmate(2-) anion.

The asymmetric units of the isostructural compounds (1,4,8,11-tetra-aza-cyclo-tetra-decane-κ )nickel(II) tetra-iodido-cadmate(II), [Ni(CHN)][CdI] (), and tri-iodido-1κ -μ-iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-2κ )cad-mium(II)zinc(II), [CdZnI(CHN)] () (CHN = 1,4,8,11-tetra-aza-cyclo-tetra-decane, cyclam, ), consist of the centrosymmetric macrocyclic cation [()] [ = Ni or Zn] with the metal ion lying on a twofold screw axis, and the tetra-iodo-cadmate anion [CdI] located on the mirror plane. In , the anion acts as an uncoordinated counter-ion while in it is bound to the Zn atom one of the iodide atoms, thus forming an electroneutral heterobimetallic complex [Zn()(CdI)]. The Ni and Zn ions are coordinated in a square-planar manner by the four secondary N atoms of the macrocyclic ligand , which adopts the most energetically stable -III conformation.

Syntheses and structural characterizations of the first coordination polymers assembled from the Ni(cyclam) cation and the benzene-1,3,5-tri-carboxyl-ate linker.

The asymmetric unit of -poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)]-μ-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ : ] octa-hydrate], {[Ni(CHO)(CHN)]·8HO} (), consists of a macrocyclic Ni cation, a carboxyl-ate dianion and eight highly disordered water mol-ecules of crystallization. The components of the compound -poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)]-μ-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ : ] monohydrate], {[Ni(CHO)(CHN)]·HO} (), are two crystallographically unique centrosymmetric macrocyclic dications, a carboxyl-ate dianion and one water mol-ecule of crystallization. In each compound, the metal ion is coordinated in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable -III conformation, and two mutually O atoms of the carboxyl-ate anions in a slightly tetra-gonally distorted -NiNO octa-hedral geometry.

Synthesis and crystal structure of di-aqua-(1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)zinc(II) bis-(hydrogen 4-phospho-natobiphenyl-4'-carboxyl-ato)(1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)zinc(II).

In the asymmetric unit of the title compound, -di-aqua-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )zinc(II) -bis-(hydrogen 4-phospho-natobiphenyl-4'-carboxyl-ato-κ)(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )zinc(II), [Zn(CHN)(HO)][Zn(CHOP)(CHN)], both Zn atoms lie on crystallographic inversion centres and the atoms of the macrocycle in the cation are disordered over two sets of sites. In both macrocyclic units, the metal ions possess a tetra-gonally elongated ZnNO octa-hedral environment formed by the four secondary N atoms of the macrocyclic ligand in the equatorial plane and the two O atoms of the water mol-ecules or anions in the axial positions, with the macrocyclic ligands adopting the most energetically favourable -III conformation. The average Zn-N bond lengths in both macrocyclic units do not differ significantly [2.

Synthesis and crystal structure of -di-aqua(1,4,8,11-tetra-aza-undeca-ne)copper(II) isophthalate monohydrate.

In the title hydrated mol-ecular salt, [Cu(CHN)(HO)](CHO)·HO, the metal ion is coordinated by the two primary and two secondary N atoms of the amine ligand and the mutually O atoms of the water mol-ecules in a tetra-gonally distorted octa-hedral geometry. The average equatorial Cu-N bond lengths (2.013 and 2.

Synthesis and crystal structure of bis-[-di-aqua-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)] -(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )bis-[4,4',4''-(1,3,5-tri-methyl-benzene-2,4,6-tri-yl)tris-(hydrogen phenyl-phospho-nato-κ)]nickel(II) deca-hydrate.

The components of the title compound, [Ni(CHN)(HO)][Ni(CHN)(CHOP)]·10HO are two centrosymmetric [Ni(CHN)(HO)] dications, a centrosymmetric [Ni(CHN)(CHOP)] tetra-anion and five crystallographically unique water mol-ecules of crystallization. All of the nickel ions are coordinated by the four secondary N atoms of the macrocyclic cyclam ligands, which adopt the most energetically stable -III conformation, and the mutually O atoms of either water mol-ecules in the cations or the phospho-nate groups in the anion in a tetra-gonally distorted NiNO octa-hedral coordination geometry. Strong O-H⋯O hydrogen bonds between the protonated and the non-protonated phospho-nate O atoms of neighboring anions result in the formation of layers oriented parallel to the plane, which are linked into a three-dimensional network by virtue of numerous N-H⋯O and O-H⋯O hydrogen bonds arising from the -NH groups of the macrocycles, phospho-nate O atoms and coordinated and non-coordinated water mol-ecules.

Crystal structures of Zn(cyclam)I (second monoclinic polymorph) and Zn(cyclam)I(I).

The asymmetric unit of the first title compound iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )zinc(II) iodide, [ZnI(CHN)]I, , consists of the zinc-cyclam macrocyclic cation with one iodide anion coordinated to the metal ion [Zn-I = 2.6619 (5) Å] and the second present as a counter-ion. The asymmetric unit of the second title compound iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )zinc(II) triiodide, [ZnI(CHN)]I, , consists of half of the centrosymmetric macrocyclic cation, in which the Zn ion coordinated to an iodide anion [Zn-I = 2.

Crystal structure of -di-aqua-(1,4,8,11-tetra-aza-undeca-ne)nickel(II) bis-(pyridine-2,6-di-carboxyl-ato)nickel(II).

The asymmetric unit of the title compound, -di-aqua-(1,4,8,11-tetra-aza-undecane-κ , , , )nickel(II) bis-(pyridine-2,6-di-carboxyl-ato-κ ,, )nickel(II) {[Ni()(HO)][Ni(pdc)] where = 1,4,8,11-tetra-aza-undecane (CHN) and pdc = the dianion of pyridine-2,6-di-carb-oxy-lic acid (CHNO )} consists of an [Ni()(HO)] complex cation and a [Ni(pdc)] anion. The metal ion in the cation is coordinated by the four N atoms of the tetra-amine ligand and the mutually O atoms of the water mol-ecules in a tetra-gonally elongated octa-hedral geometry with the average equatorial Ni-N bond length slightly shorter than the average axial Ni-O bond [2.087 (4) 2.

Crystal structure of [{[Ni(CHN)][Ni(CN)]}·2HO] , a one-dimensional coordination polymer formed from the [Ni(cyclam)] cation and the [Ni(CN)] anion.

The asymmetric unit of the title compound, -poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)]-μ-cyanido-κ :-[bis-(cyanido-κ)nickel(II)]-μ-cyanido-κ :] dihydrate], {[Ni(CN)(CHN)]·2HO] or [{[Ni(CHN)][Ni(CN)]}·2HO] , consists of a pair of crystallographically non-equivalent macrocyclic cations and anions. The nickel(II) ions (all with site symmetry ) are coordinated by the four secondary N atoms of the macrocyclic ligands, which adopt the most energetically stable -III conformation, and the mutually N atoms of the tetra-cyano-nickelate anion in a slightly tetra-gonally distorted NiN octa-hedral coordination geometry. The [Ni(CN))] anion exhibits a bridging function, resulting in the formation of parallel polymeric chains running along the [10] direction.

Crystal structure of the one-dimensional coordination polymer formed by the macrocyclic [Ni(cyclam)] cation and the dianion of di-phenyl-silanediylbis(4-benzoic acid).

The asymmetric unit of the title compound, -poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)]-μ-4,4'-(di-phenyl-silanedi-yl)dibenz-o-ato-κ :'] sesquihydrate], {[Ni(CHOSi)(CHN)]·1.5HO} , consists of the halves of the centrosymmetric macrocyclic cation and the -symmetric di-carboxyl-ate dianion and of the water mol-ecule of crystallization. The Ni ion is coordinated by the four secondary N atoms of the macrocyclic ligand characterized by the most energetically favourable -III conformation and two mutually O atoms of the carboxyl-ate, forming a slightly tetra-gonally elongated -NO octa-hedron.

A 2D coordination polymer assembled from a nickel(II) tetraazamacrocyclic cation and 4,4'-(dimethylsilanediyl)diphthalate(3-) linker.

The preformed nickel(II) complex of the 14-membered macrocyclic ligand 1,4,8,11-tetraazacyclotetradecane (cyclam, L), when treated with 4,4'-(dimethylsilanediyl)diphthalic acid (HA) in a DMF/HO mixture (4:1 v/v) under heating, leads to [Ni(L)](HA)·3DMF (I·DMF). Redissolution of this compound in a DMF/HO/MeOH mixture (4:1:30 v/v/v) with mild acidification under gentle heating results in the formation of a similar compound but containing water and methanol molecules of crystallization, [Ni(L)](HA)·5HO·2MeOH (II·HO). At lower temperature and concentration of reactants and longer reaction time, single crystals of composition {[{Ni(L)}(HA)]·4CHOH} (II·MeOH) were isolated.

Syntheses and crystal structures of the one-dimensional coordination polymers formed by [Ni(cyclam)] cations and 1,3-bis-(3-carb-oxy-prop-yl)tetra-methyl-disiloxane anions in different degrees of deprotonation.

The asymmetric units of the title compounds, namely, -poly[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)]-μ-1,3-bis-(3-carboxyl-ato-prop-yl)tetra-methyl-disiloxane-κ :'], [Ni(CHOSi)(CHN)] (), and -poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )nickel(II)]-μ-4-({[(3-carb-oxy-prop-yl)di-methyl-sil-yl]-oxy}di-methyl-sil-yl)butano-ato-κ :'] per-chlorate], {[Ni(CHOSi)(CHN)]ClO} (), consist of one (in ) or two crystallographically non-equivalent (in ) centrosymmetric macrocyclic cations and one centrosymmetric dianion (in ) or two centrosymmetric monoanions (in ). In each compound, the metal ion is coordinated by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable -III conformation, and the mutually O atoms of the carboxyl-ate in a slightly tetra-gonally distorted -NiNO octa-hedral coordination geometry. The crystals of both types of compounds are composed of parallel polymeric chains of the macrocyclic cations linked by the anions of the acid running along the [101] and [110] directions in and , respectively.

The first structural characterization of the proton-ated aza-cyclam ligand in -poly[[[(perchlorato)copper(II)]-μ-3-(3-carb-oxy-prop-yl)-1,5,8,12-tetra-aza-3-azonia-cyclo-tetra-deca-ne] bis-(per-chlorate)].

The asymmetric unit of the title com-pound, -poly[[[(perchlorato-κ)copper(II)]-μ-3-(3-carb-oxy-prop-yl)-1,5,8,12-tetra-aza-3-azonia-cyclo-tetra-decane-κ , , , ] bis-(per-chlorate)], {[Cu(CHNO)(ClO)](ClO)} , (I), consists of a macrocyclic cation, one coordinated per-chlorate anion and two per-chlorate ions as counter-anions. The metal ion is coordinated in a tetra-gonally distorted octa-hedral geometry by the four secondary N atoms of the macrocyclic ligand, the mutually O atoms of the per-chlorate anion and the carbonyl O atom of the protonated carb-oxy-lic acid group of a neighbouring cation. The average equatorial Cu-N bond lengths [2.

Crystal structures of -di-aqua-(3--1,3,5,8,12-penta-aza-cyclo-tetra-deca-ne)copper(II) isophthalate hydrates ( = benzyl or pyridin-3-ylmethyl).

The asymmetric units of the title compounds, -di-aqua-(3-benzyl-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ , , , )copper(II) isophthalate monohydrate, [Cu(CHN)(HO)](CHO)·HO, (I), and -di-aqua-[3-(pyridin-3-ylmeth-yl)-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ , , , ]copper(II) iso-phthalate 0.9-hydrate, [Cu(CHN)(HO)](CHO)·0.9HO, (II) consist of one di-aqua macrocyclic cation, one di-carboxyl-ate anion and uncoordinated water mol-ecule(s).

Crystal structure of -di-aqua-(3,10-dimethyl-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne)copper(II) pamoate.

The asymmetric unit of the title compound, -di-aqua-(3,10-dimethyl-1,3,5,8,10,12-hexa-aza-cyclo-tetra-decane-κ , , , )copper(II) 4,4'-methyl-ene-bis(3-hy-droxy-naphthalene-2-carboxyl-ate), [Cu(CHN)(HO)](CHO) {[Cu()(HO)](pam), where = 3,10-dimethyl-1,3,5,8,10,12-hexa-aza-cyclo-tetra-decane and pam = dianion of pamoic acid} consists of two independent halves of the [Cu()(HO)] cation and one di-carboxyl-ate anion. The Cu atoms, lying on inversion centres, are coordinated by the four secondary N atoms of the macrocyclic ligands and the mutually O atoms of the water mol-ecules in a tetra-gonally elongated octa-hedral geometry. The average equatorial Cu-N bond length is significantly shorter than the average axial Cu-O bond length [2.

Palladium Complexes of N,N'-Bis(2-aminoethyl)oxamide (HL): Structural (PdL, PdL, and PdLCl), Electrochemical, Dynamic H NMR, and Cytotoxicity Studies.

The monomeric (PdL·2HO) and dimeric (PdL·7HO) palladium(II) complexes of N,N'-bis(2-aminoethyl)oxamide (HL) were isolated, and their structures were established by single-crystal X-ray diffraction. Both compounds display identical cis-(2N + 2N) coordination environments of the metal ion. The dimer, representing a combination of two PdL species with an open lateral chelate ring, has an "open clamshell"-like structure.

Catenation control in the two-dimensional coordination polymers based on tritopic carboxylate linkers and azamacrocyclic nickel(II) complexes.

Four new coordination polymer frameworks, namely [(NiL(1))(3)(BTB)(2)]·6H(2)O, [(NiL(2))(3)(BTB)(2)]·6H(2)O, [(NiL(3))(3)(BTB)(2)]·6H(2)O and [(NiL(2))(3)(BTC)(2)]·10.25H(2)O (L(1) = 1,4,8,11-tetraazacyclotetradecane, L(2) = 3-methyl-1,3,5,8,12-pentaazacyclotetradecane, L(3) = 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane, BTC(3-) = benzene-1,3,5-tricarboxylate, BTB(3-) = 4,4',4''-benzene-1,3,5-triyl-tribenzoate) were prepared in water-N,N-dimethylformamide solutions. The molecular and crystal structures of these compounds are compared to the related coordination polymers formed by nickel(II) macrocyclic cations to examine the effect of carboxylate linker size on the framework architecture.

Syntheses, solid state and solution structures of the palladium(II) complexes of malonamide-derived open-chain and macrocyclic ligands.

The crystal structures of the palladium(II) complexes of the open-chain and macrocyclic ligands PdL(1).3H(2)O, PdL(2).6H(2)O and PdL(3).

Crystal and molecular structures of related nickel(II) complexes of open-chain and macrocyclic oxamide-based ligands and the peculiarities of water aggregates in their crystal lattices.

A comparison of the molecular structure of related nickel(II) complexes of the open-chain and 13-membered macrocyclic oxamide-derived ligands NiL(1).4H2O and NiL(2).3H2O revealed that the formation of an additional 6-membered chelate ring in the complex results in rather small changes in the molecular structure of the ligands and the bite angles around the metal ion.

Encapsulation of cyanometalates by a tris-macrocyclic ligand tricopper(II) complex: syntheses, structural variation, and magnetic exchange coupling pathways.

The reaction of [M(CN)(6)](3-) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and [M(CN)(8)](4-/3-) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] ([Cu(3)(L)](6+)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, [Cu(3)(L)](6+) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)][M(CN)(6)](2)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated [M(CN)(6)](3-) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units.

Structural properties of cyclopentanone-bridged bis-macrocyclic ligand dicopper(II) complexes in the solid and in solution: a successful test of the MM-EPR method.

The copper(II)-assisted condensation of 2,3,2-tet (3,7-diazanonane-1,9-diamine) with formaldehyde and cyclopentanone yields the mono- and bis-macrocyclic Mannich condensation products L(1) and L(2), as well as the Schiff-base product L(3), all with cyclam-type tetraaza macrocycles, coordinated to copper(II). The combination of molecular mechanics and EPR spectroscopy (MM-EPR) reveals that all three isomers of [Cu(2)(L(2))(OH(2))(n)](2+) (n = 0-4), with the expected trans-III (R,R,S,S) configuration of the 14-membered tetraaza macrocycles, are of similar stability, and that the isomer whose structure is solved by X-ray crystallography has a different structure in solution.