One-dimensional Zigzag Coordination Research Articles

Cd-Ln (Ln = Pr, Sm, Yb and Nd) heteronuclear complexes based on the linear chain ether Schiff base: Structural regulation and fluorescence properties

Four structurally different Cd-Ln heteronuclear complexes based on the linear chain ether Schiff base ligand (bis(3-methoxysalicylidene)-3-oxapentane-1,5-diamine (H2L) and the co-ligands 4,4′-bipyridine (bipy) or isonicotinate (IN), with composition [PrCd2L2(CH3COO)2](NO3)·CH2Cl2 (1), {[SmCdL(bipy)(NO3)3]·CH2Cl2·CH3CH2OH}n (2), [YbCdL(IN)(NO3)(CH3COO)]n (3) and {[Nd2Cd2L2(IN)2(NO3)2(CH3OH)2(CH3COO)](NO3)}n (4), have been synthesized by interfacial diffusion methods. Structural regulation is achieved by changes in the co-ligands or Ln(III) ions of different radii: Single crystal X-ray analysis determined that 1 is a trinuclear cluster with the Pr(III) ion as a joint bridging of two CdL coordination units; 2 and 3 are both infinite one-dimensional zigzag coordination polymers consisting of CdLnL secondary units through coordination bridging bipy or IN; 4 is a two-dimensional graphene laminate structure formed by two types of CdNdL secondary units bridged by both IN and acetate simultaneously. In the solid state, the complexes 1–4 all exhibit fluorescence peaks based on H2L with blue shift and enhancement. The order of fluorescence peaks intensity of the complexes in N,N-dimethylformamide (DMF) solution is consistent with that in the solid state. Moreover, the corresponding characteristic emissions of Sm(III) ion in complex 2 can be observed in the fluorescence spectra in either solid state and DMF solution, indicating that [CdL] unit is suitable for the sensitization of Sm(III) ion.

Unexpected Solvent-Dependent Self-Assembly of Alkali Metal Complexes of Calix[6]-mono-crown-4: Dinuclear Bowls, a Pseudo-Capsule, and a One-Dimensional Polymer.

1,4-Bridged calix[6]-mono-crown-4 (H4L) capable of metal binding was employed, and the influence of solvent variations on the formation of alkali metal complexes (1-6) was investigated. In the crystal, the bowl-shaped H4L host contains one water molecule in a good-fit fashion via H-bonds. When the H4L host was reacted with alkali metal hydroxides (M = Na, K, Rb, and Cs) in chloroform/methanol (solvent A), anion-free dinuclear bowl-shaped complexes of type [M2(H2L)] were isolated regardless of the metal ions. In the dinuclear bowl complexes 1-4, two metal ions (M1 and M2) show different binding behaviors: one (M1) locates inside the pocket like an "egg-in-nest", and the other (M2) positions above the M1 interacting with the calix rim. When chloroform/acetonitrile (solvent B) was used in potassium(I) complexation, interestingly, an elegant pseudo-capsule-type quadrunuclear complex 5 was isolated. In 5, two dipotassium(I) bowls in a rim-to-rim arrangement are triply bridged by one water and two acetonitrile molecules like a magic glue. However, in dichloromethane/methanol (solvent C), cesium(I) yielded an infinite product 6 in which dicesium(I) bowls are linked by cation-π interactions, giving rise to a one-dimensional zigzag coordination polymer. Taken collectively, all products share a dinuclear bowl unit, some of which are further extended to the pseudo-capsule or polymeric array, depending on the solvents. The results suggest the solvent variation as a versatile engineering tool and present a perspective on the metallosupramolecules of calix[6]-mono-crowns with monomer, dimer (e.g., pseudo-capsule), and polymer topologies.

Synthesis, characterization and exploration of supramolecular interactions of a Cu(II) based 1D zig-zag coordination polymer: X-ray structure determination and DFT study

A novel Cu(II) based one-dimensional (1D) zig-zag coordination polymer (CP) formulated as [Cu(muco)(4,4′-Me2bpy)(H2O)]·2H2O (1; H2muco = trans, trans-1,3-butadiene-1,4-dicarboxylic acid or trans, trans-muconic acid and 4,4′-Me2bpy = 4,4′-dimethyl-2,2′-bipyridine) was synthesized in a self-assembly reaction using slow evaporation technique. Single crystal X-ray analysis reveals that the compound 1 crystallizes in the triclinic system, space group Pī witha = 9.7436(12) Å,b = 11.1836(14) Å,c = 11.5063(14) Å; α = 61.520(1)°, β = 85.019(1)°, γ = 66.864(1)° and V = 1005.6(2) Å3. Its structure is composed of Cu(II) centres with a distorted square pyramidal configuration interconnected by muco ligand in an array to generate zig-zag chain. A three- dimensional (3D) supramolecular network is formed among 1D chains of 1 via hydrogen bonding and π··π interactions. Interestingly, the connectivity of lattice water molecules shows a water dimer cluster, which further undergoes hydrogen bonding along with coordinated water molecules and oxygen atoms of muco ligands to generate an octameric cluster with chair-like hexameric unit. The excellent coordinating characteristics of muco and bipyridine ligands owing to non-covalent interactions to stabilize compound1have been investigated by means of Hirshfeld analysis. The density functional theory (DFT) study is performed to calculate the HOMO-LUMO gap which enlightens the possible future application of 1 as a semiconducting device. The theoretical findings are also validated experimentally by band gap calculation utilising Tauc’s plot exploring the UV data.

Structures, fluorescence, and superoxide radical scavenging activities of two cd–Ln (Ln = Gd, Er) coordination polymers with an open-chain ether Schiff base and isonicotinate

Two Cd–Ln coordination polymers (CPs), with the open-chain ether Schiff base bis(5-bromine-3-methoxysalicylidene)-3-oxapentane-1,5-diamine (H2L), {[CdLnL(OAc)(NO3)(CH3OH)(isonicotinate)]·(3CH2Cl2)}n (Ln = Gd (1) and Er (2)), have been synthesized by the interfacial diffusion method. The structure analysis reveals that both CPs 1 and 2 are infinite one-dimensional zigzag coordination polymers, which are formed by isonicotinate bridging CdLnL cluster units. The fluorescence properties of H2L, 1 and 2 in the solid-state were studied. Compared with the free H2L, the fluorescence peaks of the two Cd–Ln CPs have undergone a significant blue shift (about 80 nm) and enhancement. This is due to the increased rigidity of the ligand after coordination of the metal ions with the ligand, which reduces the energy loss of thermal vibration. The fluorescence enhancement of 1 is greater than that of 2, which may be caused by the lanthanide contraction. Moreover, the results of experiments in vitro indicate that H2L, 1 and 2 have good ability to scavenge superoxide radical and that 1 and 2 are higher than free H2L, where their IC50 value is in the range 12.5–21.4 μM.

Syntheses, Crystal Structures, and Properties of Two d10 Metal Complexes Based on Ferrocenyl Ligands Bearing Pyrazolyl Pyridine Substituents

Two new complexes, namely, [Cd2(L1)2(NCS)4(DMF)2] · 4H2O (I) and {[Zn3(L2)4(SO4)3(H2O)8] · 3DMF · 6H2O} n (II) have been synthesized through self-assembly of Cd(II) or Zn(II) salts with ferrocenyl ligands bearing pyrazolyl pyridine substituents. The two compounds were characterized by IR spectra, element analysis, X-ray powder diffraction, single-crystal X-ray diffraction (СIF files CCDC nos. 949526 (I), 949527 (II)), and thermogravimetric analysis. Complex I crystallizes in the monocline space group P21/c and exhibits a discrete dinuclear structure. The adjacent dinuclear molecules are packed into a 1D linear chain through the hydrogen-bond interactions. Complex II is a neutral one-dimensional infinite zigzag coordination chain. The 3D packing diagram of II contains two types of voids and the solvated DMF and water molecules filled them and stabilized by the hydrogen bonds. In addition, the redox properties of both complexes I and II have also been investigated.

Discrete and polymeric supramolecular architectures derived from dinuclear oxovanadium(IV) complexes of aryl-linked bis-diketonato ligands and nitrogen donor co-ligands

Reaction of vanadyl sulfate in aqueous ethanol in the presence of sodium acetate (as base) with the 1,3-aryl-linked bis-β-diketone H2 L 1 resulted in two dinuclear isomeric complexes of type cis- and trans-[(VO)2 L 2 ]·0.5H2O that differ in the respective orientations of the oxo groups with respect to the main coordination plane in each complex. Hierarchical adduct formation by each isomer was investigated employing pyridine (py), 4,4′-bipyridine (bpy) and pyrazine (pyz) as co-ligands. Recrystallisation of either cis- or trans-[(VO)2(L 1 )2] from pyridine resulted in each case in the corresponding cis bis-pyridine adduct in which both pyridine ligands are coordinated on the same side of the V2 L 2 plane, with the vanadium(IV) centres achieving six-coordination. In contrast, when 4,4′-bipyridine in chloroform was reacted with both isomers and the solutions allowed to evaporate slowly, then a one-dimensional zigzag coordination polymer of type {trans-[(VO)2(L 1 )2(bpy)]·8CHCl3} n was isolated in each case. Each metal centre is again six-coordinate with the oxo groups oriented trans with respect to the mean V2 L 2 plane (with the bound pyridyl groups also positioned trans). In parallel experiments when diethyl ether vapour was allowed to diffuse into the respective chloroform solutions then a different, but structurally related, stepped polymer, {trans-[(VO)2(L 1)2(bpy)]·2CHCl3} n , was isolated. Reaction of either cis- or trans-[(VO)2(L 1 )2] with pyrazine followed by slow evaporation produced the same product, identified as {cis-[(VO)2(L 1 )2(pyz)]}2·4CHCl3·MeCN. In this case two planar dinuclear metallocyclic units are bridged by two pyrazine ligands such that the overall structure is a discrete tetranuclear species.

Nanoscale Permanent Rings in Two- or Three-Dimensional Structure Constructed by the Self-Assembly of Copper(II)-Macrocyclic Complexes and Tetracyanonickelate(II)

Self-assembly of polyazamacricyclic complexes of copper(II), [Cu(H2L1]4+, where L1 = 1,8-bis(2-aminoethyl)-1,3,6,8,13-hexaazacyclotetradecane, and [Cu(H2L2)]2+, where L2 = 1,8-bis(4-butylic acid)-1,3,6,8,13-hexaazacyclotetradecane, [Ni(CN)4]2- produces two-dimensional permanent ring structure (1) and three-dimensional network structure (2), respectively, in crystalline solid. The geometry around copper(II) ion is an z-elongated octahedron (1) and square pyramid (2). Inter molecular hydrogen bonding of 1 produces one-dimensional ring chain and 2 produces one-dimensional zig-zag shape coordination polymer. Hydrogen bonding of neighboring chains of 1 produces two-dimensional permanent ring structure with a nanoscale area and that of 2 produces three-dimensional network structure having one-dimensional channels with nanoscale cross-section in crystalline solid.

Assembly of Silver(I) Complexes of Isomeric NS2-Macrocycles Displaying Cyclic Oligomer, Helix, and Zigzag Structures

An isomeric series of NS2-macrocycles, incorporating ortho- (o-L), meta- (m-L), and para-xylyl (p-L) groups in their backbones between the sulfur donors, have been synthesized. A comparative investigation of the coordination behavior of these macrocyclic ligands with silver(I) salts is reported. The X-ray structures of six complexes (1–6) were determined, and a variety of structural types that range from cyclic oligomers to zigzag or helical chains is shown to occur. Reactions of o-L with silver nitrate and perchlorate afforded three complexes with different topologies: the cyclic hexamer [Ag6(o-L)6](NO3)6·0.5DMF·7H2O (1), the cyclic hexamer with two terminal complex units [Ag8(o-L)8](ClO4)8 (2), and a one-dimensional (1D) zigzag coordination polymer of type {[Ag2(o-L)2](ClO4)2·2CH3CN·CHCl3}n (3). Reaction of m-L with silver(I) perchlorate gave the 1D zigzag coordination polymer, {[Ag(m-L)]ClO4·CH2Cl2}n (4). Reaction of p-L with silver perchlorate yielded a crystalline product whose X-ray analysis confirm...

Lanthanide borohydrides supported by an ansa-bis(amidinate) ligand with a rigid naphthalene linker: Synthesis, structure and catalytic activity in ring-opening polymerization of lactide

The reactions of Ln(BH4)3(THF)2 with an equimolar amount of the dilithium derivative of a bridged bis(amidine) containing a conformationally rigid naphthalene linker afforded heterobimetallic ansa-bis(amidinate) lanthanide borohydrides [1,8-C10H6{NC(tBu)N-2,6-Me2-C6H3}2]Ln(BH4)(μ-BH4)Li(THF)2 (Ln=Nd, 2; Sm, 3). In the solid state, intermolecular contacts between the lithium atom and the terminal borohydrido groups of these compounds lead to the formation of one-dimensional zigzag coordination polymer chains. Compounds 2 and 3 are active in the ring-opening polymerization (ROP) of racemic lactide at 20°C, acting as single-site diinitiators with the two borohydride groups operative, and providing polymers with a slight heterotactic bias (Pr=0.54–0.62), controlled molecular weights and relatively narrow polydispersities (Mw/Mn=1.5–1.7).

Molecular Scaffolding of Prussian Blue Analogues Using a Phenanthroline-Extended Triptycene Ligand

Shape-persistent ligands with triptycene groups are promising candidates for the development of porous metal–organic frameworks with functional surface area. In this work, a series of phenanthroline-extended triptycene compounds was synthesized and used as structure-directing ligands for the fabrication of a triptycene-scaffolded Prussian blue analogue. The ligands were reacted with K3[Fe(CN)6] and CuCl2 under hydrothermal conditions to afford two new clathrates: a coordination compound of (triptycenyl phenanthroline) copper(I) and an infinite one-dimensional zigzag coordination polymer of copper cyanide scaffolded by phenanthroline-extended triptycenes. These structures illustrate the potential for the triptycene-functionalized ligands to provide access to materials with interesting architectures.

1,ω-Bis(pyridinium)alkane Cation as Templates for the Self-Assembly of the Mo(W)/S/Cu Polymeric Clusters

Self-assembly of a series of effective cation-templates with [Mo(W)/Cu/S]-based clusters was studied. Permanent templated products {(bppp)[MoOS3Cu3I3(4,4′-bipy)1.5]}n (1), {(bpbt)[MoOS3Cu3I3(4,4′-bipy)1.5]}n (2), {(bppp)[WOS3Cu3I3(4,4′-bipy)1.5]}n (3), and {(bpbt)[WOS3Cu3Br3(4,4′-bipy)1.5]}n (4) show 1D anionic zigzag pattern (bppp = 1,3-bis(pyridinium) propane, bpbt = 1,4-bis(pyridinium) butane). Compounds 1–4 have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, UV–vis and thermogravimetric Analysis. The results may provide fascinating insights into template effects on the construction of the cluster-based coordination polymers and that coordination modes of compounds 3 and 4 have not been found in the reported one-dimensional zigzag coordination polymers.

Structural Diversity of a Series of Mn(II), Cd(II), and Co(II) Complexes with Pyridine Donor Diimide Ligands

A series of Mn(II), Cd(II), and Co(II) metal–organic frameworks, namely, {[Mn(L1)(NCS)2(CH3OH)2]·2(CH3OH)}n (1), {[Mn(L2)2(NCS)2(CH3OH)2]}n (2), {[Mn(L3)2(NCS)2]·0.5(CH3OH)·4.5H2O}n (3), {[Cd(L1)(I)2]·3(H2O)}n (4), {[Cd(L2)(I)2]}n (5), {[Cd(L3)(NCS)2]·2.5(H2O)}n (6), {[Co(L1)2(NCS)2]·4(H2O)}n (7), {[Co(L2)2(NCS)2]·(HCCl3) }n (8), and {[Co(L3)2(NCS)2]·3(H2O)}n (9) (where L1 = N,N′-bis(4-pyridylmethyl)-pyromellitic diimide, L2 = N,N′-bis(3-pyridylmethyl)-pyromellitic diimide, L3 = N,N′-bis(4-pyridylmethyl)-naphthalene diimide), were synthesized and structurally characterized by elemental analyses, thermogravimetric (TG) analyses, powder X-ray diffraction, IR spectroscopy, and single-crystal X-ray diffraction. In Mn(II) complexes 1–3, L1 connects the adjacent metal centers to form an infinite one-dimensional (1D) zigzag coordination polymeric chain, L2 acts as a monodentate ligand to give mononuclear coordination motifs, while L3 bridges two metal ions to generate two-dimensional (2D) networks of the (4, 4) ...

Assembly, crystal structures and luminescent properties of the lanthanide nitrate coordination polymers with 1,5-bis{[(2′-(2-picolylaminoformyl))phenoxyl]methyl}naphthalene

A new amide type bridging ligand, 1,5-bis{[(2'-(2-picolylaminoformyl))phenoxy]methyl}naphthalene (L), and its complexes with lanthanide ions (Ln Sm, Eu, Gd, Tb, and Dy) have been designed and assembled. The crystal structures of {[EuL(NO3)(3)(CH3OH)](H2O)}(n) and [TbL(NO3)(3)(CH3OH)](n) display one-dimensional (1-D) zig-zag coordination polymeric chains. At the same time, the solid state luminescent properties of the Sm, Eu, Tb, and Dy complexes were investigated at room temperature. The complexes all exhibit characteristic luminescence emissions of the central metal ions under UV light excitation. The lowest triplet state energy level (T-1) of the ligand indicates that the triplet state energy level of the ligand matches better to the resonance level of Tb(III) ion than other lanthanide ions. (C) 2011 Elsevier B.V. All rights reserved.

Crystal structures and luminescent properties of lanthanide nitrate coordination polymers with structurally related amide type bridging podands

A one-dimensional linear chain coordination polymer [ErL I(NO 3) 3(CH 3CO 2Et)] n (L I=1,2-bis{[(2'-furfurylaminoformyl)phenoxyl]methyl}benzene) and a one-dimensional zig-zag coordination polymer {[TbL II(NO 3) 3(H 2O)]·(H 2O)} n (L II=1,2-bis{[2'-(2-pyridylmethylaminoformyl)phenoxyl]methyl}benzene) were assembled by two structurally related bridging podands L I and L II which have uniform skeleton and different terminal groups. In {[TbL II(NO 3) 3(H 2O)]·(H 2O)} n , the neutral chains were linked by the hydrogen bonding interactions between the free and coordinated water molecules from two different directions to interpenetrate into a 3D supramolecular structure. At the same time, the luminescent properties of the solid Tb(III) nitrate complexes of these podands were investigated at room temperature. The lowest triplet state energy levels T 1 of the podands L I and L II indicate that the triplet state energy levels of the antennae are both above the lowest excited resonance level of 5D 4 of Tb 3+ ion. Thus the absorbed energy could be transferred from ligands to the central Tb 3+ ions. And the influence of the hydrogen bonding on the luminescence efficiencies of the coordination polymers was also discussed.

Zn(II) and Cd(II) Coordination Polymers Assembled from a Versatile Tecton 5-Nitro-1,2,3-benzenetricarboxylic Acid and N,N′-Donor Ancillary Coligands

Five novel zinc(II) and cadmium(II) metal−organic coordination polymers with a tricarboxyl tecton and N-donor ancillary ligands, {[Zn(Hnbta)(2,2′-bipy)]·H2O}n (1), {[Cd3(nbta)2(2,2′-bipy)2(H2O)2]}n (2), {[Cd3(nbta)2(bpa)2]}n (3), {[Zn2(nbta)(OH)(bpa)1.5]·2H2O}n (4), and {[Zn3(nbta)2(bpp)2(H2O)2]}n (5) (H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, bpa = 1,2-bi(4- pyridyl)ethane, and bpp = 1,3-bi(4-pyridyl)propane), have been prepared and characterized by elemental analysis, IR spectra, and X-ray diffraction. Complex 1 has a two-dimensional (2D) bilayer supramolecular network constructed from one-dimensional (1D) zigzag coordination chains via π···π interactions, whereas 2 exhibits a three-dimensional (3D) supramolecular network assembled from 1D coordination arrays through π···π interactions and weak C−H···O interactions. Complex 3 features a (4,5)-connected self-penetrating 3D coordination net with a (43·65·82)(43·62·8)(44·64·82)(45·65) topology. The 3D framework of 4 can...

Catena-Poly[[[triaquasulfatozinc(II)]-μ-3,3′-bis(3-pyridyl)-1,1′-(m-phenylene)diurea] methanol solvate monohydrate

In the title coordination polymer, {[Zn(SO4)(C18H16N6O2)(H2O)3]·CH3OH·H2O}n, the Zn2+ ion adopts a slightly distorted cis-ZnN2O4 octa­hedral geometry arising from three coordinated water mol­ecules, one sulfate ion and two bridging 3,3′-bis­(3-pyrid­yl)-1,1′-(m-phenyl­ene)diurea (bpmpbu) ligands. The dihedral angles between the central benzene ring and two terminal pyridine rings of the bpmbpu mol­ecule are 10.58 (17) and 34.63 (16)°. In the crystal, the ligands bridge the ZnII ions, thus generating a one-dimensional zigzag coordination polymer propagating in [010]. The crystal structure features extensive N—H⋯O and O—H⋯O hydrogen-bonding inter­actions.

Synthesis, characterisation and crystal structure of a cobalt(II)-hexamethylenetetramine coordination polymer

A novel one-dimensional zigzag coordination polymer, dinitrodiaqua-bis(hexamethylenetetramine)cobalt(II) was synthesised and characterised, and the structure was determined by single-crystal X-ray diffraction. The compound has a chain structure with each cobalt atom covalently bonded to two nitrate ions, two water molecules and two HMTA molecules, giving a slightly distorted octahedral geometry about the cobalt atom. Each HMTA ligand uses two of its N atoms to bond to two cobalt atoms giving an approximately bent Co–HMTA–Co configuration. Each chain is hydrogen bonded through OH···N and OH···O interactions with neighbouring chains leading to an overall polymer structure. Thermal studies show significant mass loss corresponding to the loss of the coordinated water molecules and the decomposition of both the nitrate ions and the HMTA.

Discrete metallocyclic complexes based on rigid pyrazole-containing ligands as building blocks to construct inorganic–organic supramolecular assemblies through the second interactions

Utilizing the new rigid bidentate pyrazole-containing ligands 1,3-bis(1-pyrazolyl)benzene (bpb) and 3,5-bis(1-pyrazolyl)phenylmethanol (bppm) with corresponding silver salts, four new compounds, [Ag 2(bpb) 2(NO 3) 2] ( 1), [Ag 2(bpb) 2(OSO 2CF 3) 2] ( 2), {[Ag 2(bpb) 2](BF 4) 2} ( 3), and [Ag 2(bppm) 2(NO 3) 2] ( 4), have been synthesized. X-ray diffraction analyses reveal that these compounds involve the discrete M 2L 2-type metallocyclic units, which serve as building blocks to further expand to various three-dimensional inorganic–organic supramolecular assemblies through the second interactions such as hydrogen bonds (e.g., O–H⋯O, C–H⋯O and C–H⋯F), π⋯π stacking and C–F⋯π interactions. Especially in compound 1, the metallocyclic units are directly connected by Ag–O–Ag bonds, which constitutes, to the best of our knowledge, the first example of inorganic–organic hybrid polymers with channels bridged by oxygen atoms from inorganic anions. Unlike 1– 4, the usage of 2,7-bis(1-pyrazolyl)naphthalene (bpn) results in the formation of one-dimensional zigzag coordination polymer chains [Ag(bpn)NO 3] ( 5) rather than the discrete metallocyclic structures, which are further bridged by nitrate anions to generate an unusual (4,4) 2-D sheet structure with quadrangle grids. The structural differences of five compounds mainly depend on the nature of organic ligands and anions. These results demonstrate that the second interactions could play important roles in the aspect of linking low-dimensional entities into high-dimensional supramolecular frameworks.

Vertical Interpenetration of 1D Water Column and 1D Coordination Polymer Chain

Hydrothermal reaction of 1-amino-1-phenylmethane-1,1-diphosphonic acid (APhMDPH4), ZnO and 2,2′-bipyridyl (2,2-bipy) affords a novel zinc phosphonate compound, i.e. Zn3(L1H)2(2,2′-bipy)3 · 18H2O (1), in which the phosphonate ligand, L1H4, is generated via an in situ concentration reaction. This compound is a one-dimensional (1D) zigzag coordination polymer chain and a huge, complex 1D water column. The 1D water column and the 1D coordination polymer chain are joined together to form a vertical interpenetrating network, which is reported for the first time.

Crystal structure and magnetic properties of the 1D bimetallic thiocyanate bridged compound: {(CuL 1)[Co(NCS) 4]}(L 1 = N- rac-5,12-Me 2-[14]-4,11-dieneN 4)

The synthesis, crystal structure and magnetic properties are reported for the new bimetallic compound {(CuL 1)[Co(NCS) 4]} where L 1 = N- rac-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The complex forms a one-dimensional zig-zag coordination polymer along the crystallographic c axis, with Co(II) and Cu(II) ions connected via thiocyanate bridges. The Co(II) centre in the [Co(NCS) 4] fragment approximates a distorted tetrahedral symmetry. The Cu(II) geometry is a distorted tetragonal bipyramid with the apical position occupied by the bridging thiocyanate ligand and the basal ones by the four nitrogen atoms from the macrocyclic ring. The polymer chain nearest Cu(1)⋯Co(1) distances are 6.4152(9) and 6.0988(9) Å and the nearest Cu(1)⋯Co(1) interchain distances are 6.8609(9), 6.9628(9) and 6.0336(10) Å. The magnetization measurements for the examined compound have been carried out over the range 1.8–300 K. This data suggest ferromagnetic interactions through the thiocyanate bridge.