From mononuclear to linear one-dimensional coordination species of copper( II ) – chloranilate: design and characterization †

A series of six novel mononuclear, binuclear and linear one-dimensional (1D) compounds of copper( II ) with chloranilic acid (3,6-dichloro-2,5-dihydroxybenzoquinone, H 2 CA) is prepared and a design strategy for the preparation of such complexes is discussed. Four described compounds are linear 1D coordination polymers [Cu(CA)] n , whereas another two involve a binuclear and a mononuclear, Cu 2 (CA) 3 and Cu(CA) 2 , core unit. A linear polymer incorporating bulky aromatic imidazole has been synthesized as a result of investigation of the in ﬂ uence of pH on the reaction mixture. Two coordination modes of the chloranilate dianion are observed. The bridging (bis)bidentate mode generates linear 1D polymeric species. Among these one reveals square-pyramidal coordination of Cu 2+ , whereas the three polymers contain Cu 2+ in an octahedral arrangement. However, the combination of both, terminal bidentate ( ortho -quinone) and bridging (bis)bidentate modes of coordination produces a binuclear complex anion, which comprises a square-pyramidal coordination of Cu 2+ complex anions forming a supramolecular honeycomb-like network encapsulating 4,4 0 -bipyridine cations. When the chloranilate dianion coordinates the Cu 2+ atom only in a terminal bidentate mode, a mononuclear complex with an octahedral environment of the metal centre is formed. The presence of the bulky ancillary ligand imidazole produces an unprecedented packing involving chiral (racemic) and achiral ( meso -compound) coordination polymers in the same crystal. Electron spin resonance spectroscopy of polycrystalline samples determined g-tensor parameters of copper( II ) ions in di ﬀ erent coordination geometries and revealed weak exchange interactions (| J | < 1 cm (cid:2) 1 ) in linear metal-complex polymers and dimeric species.


Introduction
Coordination polymers, also known as metal-organic coordination networks (MOCNs) or metal-organic frameworks (MOFs), are metal-ligand compounds having innite one-(1D), two-(2D) or three-dimensional (3D) networks through more or less covalent metal-ligand bonding.The ligand should be a bridging organic group and the metal atoms must only be bridged by this organic ligand at least in one dimension. 1,2Due to the diversity of metal species and ligands, coordination geometry, guests inside the pores, and supramolecular arrangements, a huge number of coordination polymers with different structures and pores have been synthesized and characterized; different dimensionality and topology of the metal complexes result in a variety of magnetic and/or electrical properties. 2 The magnetic properties can be designed and ne-tuned by choice of the bridging ligand; small ligand strongly affects exchange interaction and spin coupling, whereas some ligands with conjugated p-electron systems are able to mediate exchange interactions at long distances.The careful selections of the organic ligands used for a ne tuning of the physical properties lead to various applications, such as catalysis, electrical conductivity, luminescence, magnetism, non-linear optics or zeolite behaviour.4][5] Selection of the metal cation(s) offers further options for design of magnetic properties.][8][9] Besides magnetic properties, coordination polymers may possess electrical properties: conductivity, semiconductivity, ferroelectricity, etc. Electronic conductivity is possible along a polymeric chain comprising ligands with conjugated psystems.Design of such systems and ne-tuning of the interactions dening the properties, is a topic of crystal engineering. 2,10,112][13][14][15][16][17][18][19][20] They are prone to form a variety of coordination modes [19][20][21][22][23][24] and to mediate electronic effects between paramagnetic metal ions via their four oxygen donors and p-electron systems, respectively. 25sually 2,5-dihydroxyquinones are bridging (bis)bidentate ligands, but sometimes may also act as bidentate + bridging monodentate ligands, 26 with the possibility to generate polymeric complexes.Mononuclear complexes with chloranilic acid acting as a terminal bidentate ligand are known as well. 26,27ctually, 2,5-DHQs can be regarded as "extended" (i.e.sterically bulkier) version of the oxalate. 26Conjugated bonds of the quinoid ring and presence of two acidic hydroxy-groups make the electronic structure of 2,5-DHQs 26,27 uniquely malleable depending on ionisation, molecular environment, and degree of electron delocalisation characteristics; it can exist as an ortho-or para-quinoid structure, or a dianion-like structure with two separated delocalised systems (Scheme 1).Quinones are also weak oxidants, and their proton-accepting properties can be enhanced by electronegative substituents, thus enabling the charge transfer between a metal centre and the quinoid ring; the quinone is then reduced into a semiquinone radical. 28,29Their potential in design of magnetic, charge-transfer and spin-crossover materials has been little studied so far.
The rational design and optimisation of synthesis of the coordination polymers based on chloranilic acid and rst-row transition metals is the goal of our research.The use of bridging mode of CA ligand should be in favour of formation of linear Cu(II) polymeric chains due to its ability to mediate electronic effects between paramagnetic metal ions, even at large Cu/Cu separation distance (exceeding 7 Å).The size of the metal cation is an important parameter: larger cations (for example: Cr 3+ , Mn 2+ , Fe 3+ ) can better accommodate large multidentate ligands than smaller ones (Cu 2+ , Zn 2+ ).Therefore, Cu 2+ complexes with CA and bidentate N-donor ligands are almost exclusively mononuclear, 26,27 while larger cations can accommodate zig-zag 1D polymers. 22,30Linear 1D-polymers of Cu 2+ are obtained if additional bidentate ligands were replaced by solvent molecules such as water 31 and methanol 13 acting as monodentate ancillary ligands.An appropriate bridging (bis) monodentate ligand, such as pyrazine, can link the chains into a 2D network. 13

Results and discussion
We designed and prepared a series of six novel compounds: (5)  and [Cu(CA)(im) 2 ] n (6) (Scheme 1).They are studied using the Xray structural analysis, IR and ESR spectroscopies, performed to obtain spin-Hamiltonian parameters of copper(II) ions as well as the values of exchange interactions in the compounds.The dark crystals of the titled compounds were obtained by slow liquid diffusion.This layering technique was applied for the preparation of the crystals of the quality needed for X-ray analysis. 32lecular structures of compounds 1-6 The compound, 1, is a salt of a mononuclear complex anion [Cu(CA) 2 (H 2 O) 2 ] 2À (Fig. 1) with imidazole as cations (Him + ); its asymmetric unit comprises a half of the complex anion with molecular symmetry C i (Fig. 1) and a single imidazolium cation (Fig. S1 †).The central copper atom is located at an inversion centre (1/2, 0, 1/2) and its coordination is a distorted octahedron (Table S1 The compound 2 is the complex salt of a dinuclear anion with 4,4 0 -bpy cation and crystal water molecules (4,4 0 -H 2 bpy) [Cu 2 (CA) 3 (H 2 O) 2 ]$2H 2 O.Its asymmetric unit is a half of the dianion (Fig. 1) and a half of the cation (Fig. S2 †), both having a C i symmetry.The coordination of copper atom is a distorted square-pyramid with a water molecule at the apical position (Table S1 †).
In the polymer 3, [Cu(CA)(CH 3 CN)] n (Fig. 1), copper coordination is also a distorted square-pyramid (Table S1 †), where its apical position is occupied by an acetonitrile molecule.][36] The analogous compounds 4, 5 and 6 consist of linear 1D chains with chemical compositions of [Cu(CA)(H 2 O) 2 ] n , [Cu(CA)(EtOH) 2 ] n and [Cu(CA)(im) 2 ] n , respectively (Fig. 1).The Cu atom and chloranilate ring have crystallographic symmetry C i in 4 and C 2 in 5.In all these complexes, copper coordination is a distorted octahedron (Table S1 †): the metal is coordinated by two chloranilates in the equatorial position (in a trans arrangement) and two water/ethanol/imidazole molecules occupying two apical positions.Previously prepared and investigated compound {[Cu(CA)(H 2 O) 2 ]$H 2 O} n (ref.31) contains the same polymeric unit as our compound 4, however, it is a monohydrate, while we report the structure without a crystal water.
In 6 exist two symmetry-independent chains (designated as A and B; Fig. 1), both parallel to [010] direction.The chain A is C 2symmetric, with twofold axis passing through Cu atoms and midpoints of chloranilate rings.It is therefore chiral, with both R and S enantiomers (Scheme 2) present due to the centrosymmetric space group.The chain B is centrosymmetric, with Cu atoms and chloranilate rings having a crystallographic symmetry C i .It can be regarded as a meso-compound, and differs from its diastereomer A in orientation of imidazole ligands, as seen in Fig. 2 and Scheme 2. This is a rare example of co-crystallization of a chiral and a meso-molecule. 37n four prepared polymers chloranilate dianions act as bridging (bis)bidentate ligands, and have dianion-like geometry with two delocalized systems separated by two single C-C bonds (Scheme 1 and Table 1).In compounds 1 and 2, two chloranilates act as terminal bidentate ligands and have an orthoquinone-like geometry, while the central one in 2 acts as a bridging (bis)bidentate ligand and has dianion-like characteristics (Table 1). 26,27So far, only a few compounds are known that comprise two different coordination modes of chloranilic acid, 15,17,24,[38][39][40] which could be easily distinguished by IR spectra.
Generally, the positions of the symmetric and asymmetric carboxylate stretching vibrations in the IR spectrum are indicative of the binding mode of the ligand.Selected absorption bands ascribed to the vibrations of the bidentate 26,27 and bis-(bidentate) 11,[41][42][43] chloranilate anion for compounds 1-6 are given in Table 2.In terminal bidentate ligand, single and double C-O bonds can be distinguished, 26,27 with their respective stretching vibrations close to the neutral chloranilic acid. 44,45In the case of bridging (bis)bidentate ligand, whose structure is similar to that of the free dianion, only one type of the stretching vibration of the C-O bond is present in the   spectrum, consistent with bond length about 1.26 Å (in between single and double bond, Table 1).The spectra of 1 and 2 demonstrate some differences (Table 2); in compound 1 chloranilate anion has bidentate coordination mode so stretching vibrations of n(C-O) and n(C]O) could be observed, while in compound 2, having bidentate and bridging bis(bidentate) chloranilate anions, n(C-O), n(C]O) and n(C/O).In compounds 3-6 chloranilate anion is bridging and only [n(C/ O)] is found (Table 2).In the spectra of compounds 1, 2 and 6 other absorption bands of signicant intensities correspond to different vibrations of the imidazole and 4,4 0 -bipyridine molecules. 46ystal packing of compounds 1-6 In compound 1 complex anions [Cu(CA) 2 (H 2 O) 2 ] 2À form hydrogen bonded layers parallel to (110), which are linked through imidazolium cations into a 3D network (Fig. 3a, Table 3).There are innite p-stacks parallel to [001]: stacks of chloranilate moieties stabilise the anionic layers, whereas the imidazolium cations form their own stacks (Fig. 3b, Table 4).This structure came as a surprise, since imidazole was intended as a ligand (due to its two nitrogens, it may be able to link the [CuCA] n chains, similar to pyrazine 13 ), rather than a counter-ion; however, its coordination to Cu 2+ required a more basic solution.
Packing of 2 reveals a 3D network realised through seven symmetry-independent hydrogen bonds (Table 3).Complex anions [Cu 2 (CA) 3 (H 2 O) 2 ] 2À and uncoordinated water molecules form a porous honeycomb-like structure (Fig. 4a) which is further stabilised by p-stacking of the anions in the direction [100] (Fig. 4b, Table 4).Cations of 4,4 0 -bpy ll in the voids (Fig. 4a) and they are linked into water-anion network by Table 1 Bond lengths in the chloranilate anion (Å) in compounds 1-6.Symmetry operator (i) is an inversion and (ii) is a rotation about a twofold axis.Crystallographic symmetry of the anion in 1, 2 (central bridging ligand) and 4 is C i , in 2 (terminal) and N-H/O hydrogen bonds (Table 3).The rationale behind use of 4,4 0 -bpy was that it may occupy apical positions in the Cu coordination sphere, linking the linear polymers into the layers, similar to the previously known pyrazine complex, [Cu(CA)(pyz)] n . 13owever, basicity of 4,4 0 -bpy is too high, so it gets protonated in the presence of moderately strong chloranilic acid (its pK a values being 0.76 and 3.08, respectively 47 ), therefore it is present in the compound in the cationic state.Attempts of moderating pH of the aqueous medium by use of a weak, non-complexing base such as ammonia, yielded no single crystals suitable for X-ray measurement, and the obtained samples were too inhomogeneous and impure to allow any meaningful analysis.Due to the presence of the 4,4 0 -bpy cations, the innite neutral [Cu(CA)] n chains (as present in studied compounds 3-6) did not form; instead, discrete dianionic complexes, balancing the charge of the 4,4 0 -bpy cations, were obtained.However, it is worth nothing that the anions [Cu(CA)   the case of 1 and 2 growth of chains was probably terminated due to the presence of the cations.Innite chains of 3 extend in the direction [100] (Fig. 5a); the square-pyramidal coordination of Cu centres allows close contact between planar delocalised quinoid and chelate rings, so two chains stack into pairs by p-interactions (Fig. 5b, Table 4).][50][51][52] There are also C-H/O hydrogen bonds which link the pairs of chains into layers parallel to (011) (Fig. 5a, Table 3).
In crystal packing of 4 and 5 linear 1D coordination polymers are extended in the directions [100] (Fig. 6 and 7).
Since octahedral coordination of Cu centres prevents close contact between p-systems, there are no stacking interactions and crystal packing is realised through O-H/O and O-H/Cl hydrogen bonding.Due to steric similarities and existence of inter-chain hydrogen bonding (there are two symmetry-independent hydrogen bonds in both compounds, Table 3), the comparison of their crystal packing (Fig. 6 and  7) reveals inter chain hydrogen bonds in 4 generate a 3D hydrogen-bonding network, while in 5 there are hydrogenbonded layers.The previously published hydrate of 4, {[Cu(CA) (H 2 O) 2 ]$H 2 O} n , 31 also forms a 3D network; its packing includes uncoordinated water molecule linking the chains, rather than direct hydrogen bonding between the chains.Crystal packing of 6 is generally similar to packing of 4 and 5: polymeric chains are hydrogen bonded into a 3D network (Fig. 8, Table 3).Imidazole ligands of A chains are proton donors towards chloranilate oxygens of B chains and vice versa, forming layers parallel to (110); additionally the layers are stabilised by p-interactions between imidazole ligands (Fig. 8, Table 4).A 3D network is achieved by linking the layers through N-H/O hydrogen bonds (Table 3).

ESR spectroscopy
The electron spin resonance (ESR) spectra were recorded from liquid nitrogen temperature up to room temperature (RT) and the representative spectra, obtained at T ¼ 80 and 296 K, are shown in Fig. 9.The relative intensities of the spectra at low and room temperatures are presented in the real ratios, for each compound.Half-eld ESR line connected with forbidden transition DM s ¼ AE2 was not detected for any compound.To determine spin-Hamiltonian parameters of Cu 2+ ions and exchange interaction parameters, spectra simulation and linewidth consideration were performed.
The simulations were carried out by the EasySpin soware. 53o simulate spectra, the following form of spin-Hamiltonian was assumed: In eqn (1), B is magnetic eld, S is electron spin operator and g is g-tensor.Hyperne splitting tensor A, due to interaction between electron S ¼ 1/2 and nuclear spin I ¼ 3/2 in copper ions, is approximated to be zero.The simulated spectra, shown in Fig. 9, were obtained using the parameters presented in Table 5.The same parameters were used for the simulation of the spectra at low and room temperatures by taking into consideration only line-broadening effect (ESR lines were broader at higher temperatures).Line shapes used in simulation were always Lorentzian.The simulations reproduce well the experimentally observed spectra for compounds 1, 2 and 5, as could be seen in Fig. 9.The additional lines observed in spectra of compounds 3, 4 and 6 are probably connected with presence of trace impurity (i.e.electron in the vicinity of 14 N and 1 H nuclei).
Observed Lorentzian lineshapes and absence of hyperne interaction for copper(II) ions point to the presence of exchange interactions in the investigated systems.The values of exchange interaction parameters, |J|, could be approximately calculated using linewidth analysis and the method of moments: 54,55 Here, u exch $ J[S(S + 1)] 1/2 and g is gyromagnetic ratio, G exp is the experimental linewidth (G ¼ FWHM/(2 Â 1.18)) while G d is the dipolar linewidth due to the contribution of the nearest copper(II) ions. 56,57If we consider all copper ions in the sphere of radius 15 Å, the values of the dipolar linewidths are G d $ 5-25 mT.Taking into consideration experimental linewidths (values at 80 K used in the simulations) G exp $ 0.7-2.6 mT, exchange interaction parameters, |J|, were calculated and presented in Table 5.The values calculated in this way have approximate accuracy, but from Table 5 it could be seen that weak exchange interaction are found for all compounds (|J| < 1 cm À1 ).
The obtained axial g-tensors with g z > g x ¼ g x reveal that the ground state of unpaired electron is the d x 2 Ày 2 orbital, for compounds 2 and 5. Other compounds show "rhombic" spectra, exhibiting three different g-values.For complexes of this type, a parameter R is the indication of the predominance of the d x 2 Ày 2 or d z 2 orbital in the ground state. 58The systems where g z > g y > g x , R parameter is dened as: For R > 1, the ground state is predominantly d z 2 , whereas for R < 1, the ground state is predominantly d x 2 Ày 2 .The obtained R parameters are shown in Table 5, indicating that the greater contribution to the ground state arises from d x 2 Ày 2 orbital.This is in agreement with the crystal structure of the compounds.Both types of observed coordination of copper atoms (a square pyramid in compounds 2 and 3 and elongated octahedron in compounds 1, 4, 5 and 6) give so called normal spectra of Cu 2+ ions (g z > g y z g x > 2.0023). 58he distance between chloranilate-bridged Cu 2+ atoms within a single molecule range between 7.6 and 8.1 Å, while the inter chain distances of the Cu 2+ atoms are considerably shorter than intrachain ones (Table 6).However, relative orientations of d x 2 Ày 2 orbitals of interacting Cu 2+ atoms are important.In 1, 2, 3 and 5, the d x 2 Ày 2 orbital is parallel to the chloranilate plane, while in 4 and 6 it lies in the plane dened by Cu-O 2 (CA) and Cu-L axial vectors, approximately normal to the chloranilate plane 9,10 (Table 1).However, in all studied compounds, orientations of d x 2 Ày 2 orbitals in neighbouring molecules are not favourable for orbital overlap. 57Therefore, weak exchange interaction is observed inside [Cu(CA)] n chains.(6).The intensities of the spectra at T ¼ 80 and 296 K are presented in the real ratios, for each compound.

Conclusions
We have prepared and characterised six novel Cu-chloranilate compounds, ranging from mononuclear to innite 1D coordination polymers.Due to small size of the Cu 2+ atom, it can accommodate two chloranilate ligands in trans-arrangement, only; according to the Cambridge Structural Database, 59 for larger rst-row transition metals the arrangement is usually cis (generating zig-zag coordination polymers).The h and sixth coordination sites can then be occupied by small monodentate ligands such as water, ethanol or acetonitrile, which do not introduce steric strain; therefore, [Cu(CA)] n coordination polymers remain linear.A bidentate ancillary ligand, such as 2,2 0bipyridine, must bind cis vs. chloranilate; in the case of the small Cu 2+ atom, it is impossible, and monomers are obtained, only. 26,27However, the bulky aromatic imidazole ligand serendipitously revealed interesting steric effects: instead of bridging, it binds to the linear [Cu(CA)] n chains as a monodentate ligand; its steric strain is compensated by its different orientations, resulting in a combination of chiral (A) and achiral meso-(B) chains.Also, cross-linking the [Cu(CA)] n polymers into a 2D network is not achieved easily, since both imidazole and 4,4 0 -bipyridine are highly basic and tend to be protonated in the presence of chloranilic acid.Raising pH of the solution by use of some common bases usually results in unwanted precipitation of alkali or ammonium chloranilate salts and/or copper hydroxyde.
In coordination polymers, copper(II) usually has a distorted octahedral coordination, and the compound 3 is a rare example of Cu-chloranilate coordination polymer with pentacoordinated Cu 2+ .Also, compound 2 is a rare example of a complex with two different modes of coordination of chloranilate, a terminal bidentate and a bridging (bis)bidentate ones.Changes of electronic structure of the 2,5-dihydroxyquinonate ring upon various coordination modes affects signicantly geometry of the chloranilate moiety.
To the best of our knowledge, so far no crystal structure comprising both a racemate and a meso-compound has been described.The compound 6 is probably the rst such example.
ESR spectroscopy gave the g-tensors for Cu(II) ions.The spectra simulations reveal d x 2 Ày 2 orbital as the ground state of unpaired electron in copper ions for compounds 2 and 5, whereas for other four compounds, due to "rhombic" spectra, the greater contribution to the ground state arises from d x 2 Ày 2 orbital.These results are in agreement with cooper coordination, which is square pyramid in the compounds 2 and 3, and elongated octahedron in other compounds.Furthermore, ESR linewidth analysis revealed the presence of weak exchange  interactions (|J| < 1 cm À1 ) between the copper ions in the investigated complexes, which is consistent with specic crystal packing and also with the values found in similar compounds. 9,10

Materials and physical measurements
The chemicals were purchased from commercial sources, and used without further purication.Infrared spectra were recorded as KBr pellets using a Bruker Alpha-T spectrometer, in the 4000-350 cm À1 range.with an ethanol solution (4 mL) of 4,4 0 -bpy (15.6 mg; 0.1 mmol), the reaction mixture became cloudy and a blue precipitate immediately formed.It was removed by ltration and the clear light green solution was carefully laid above a dark violet aqueous solution (5 mL) of H 2 CA (20.9 mg; 0.1 mmol) into a test tube.Reddish-violet prismatic single crystals of 2 were formed aer a few weeks.The yield was $31%.
[Cu(CA)(im) 2 ] n (6).Aer mixing an aqueous solution (3 mL) of CuCl 2 $2H 2 O (17.1 mg; 0.1 mmol) with an aqueous solution (2 mL) of imidazole (6.8 mg; 0.1 mmol), the pH value of the resulting solution was adjusted to pH ¼ 8 using a 25% ammonia.A blue solution than was layered with a orange ethanol solution (7 mL) of H 2 CA (20.9 mg; 0.1 mmol).The reaction mixture was le to stand undisturbed for one week to yield X-ray quality black needles.The yield was $32%.

Crystallographic data collection and renement
Single crystal measurements were performed on an Oxford Diffraction Xcalibur Nova R diffractometer (microfocus Cu tube) at RT [293(2) K].Only the symmetry-independent part of the Ewald sphere was measured.Program package CrysAlis PRO 60 was used for data reduction.The structures were solved using SHELXS97 (ref.61) and rened with SHELXL97. 61The models were rened using the full-matrix least squares renement; all non-hydrogen atoms were rened anisotropically.Hydrogen atoms bound to C atoms were modelled as riding entities using the AFIX command, while those bound to O were located in difference Fourier maps and rened with the following restraints: geometry of water molecules was restrained to d(O-H) ¼ 0.95(2) Å; d(H/H) ¼ 1.50(4) Å, and the hydroxyl group to d(O-H) ¼ 0.82(2) Å.In 2 methyl hydrogen were renes as free atoms with the following restraints: d(C-H) ¼ 0.96(2) Å; d(H/H) ¼ 1.50(4) Å.
Molecular geometry calculations were performed by PLA-TON, 62 and molecular graphics were prepared using ORTEP-3, 33 and CCDC-Mercury. 63Crystallographic and renement data for the structures reported in this paper are shown in Table 7.

ESR spectroscopy
The ESR measurements were performed on polycrystalline samples of the compounds 1-6 by an X-band Bruker Elexsys 580 FT/CW spectrometer (microwave frequency around 9.7 GHz).The measurements were carried out at the modulation frequency 100 kHz.The magnetic eld modulation amplitude was 0.5 mT (recorded also with modulation amplitude of 0.2 mT, as additional verication).The spectrometer was equipped with a standard Oxford Instruments model DTC2 temperature controller.Spectra were recorded from liquid nitrogen temperature up to RT (Fig. 9).

Scheme 1
Scheme 1 Dissociation of chloranilic acid and schematic representation of its binding to copper(II) ions investigated in this work.
b a ¼ angle between planes of two interacting rings.c b ¼ angle between Cg/Cg line and normal to the plane of the rst interacting ring.d Offset can be calculated only for the strictly parallel rings (a ¼ 0.00 ).For slightly inclined rings (a # 5 ) an approximate value is given.

Fig. 5
Fig. 5 Crystal packing of 3: (a) an arrangement of polymeric chains linked by C-H/O hydrogen bonds (dashed lines), (b) showing pairs of p-stacked rings of quinoid ligands and chelate rings (interactions between individual rings are highlighted).

Fig. 6
Fig. 6 Crystal packing of 4 showing hydrogen bonding O-H/Cl and O-H/O (dashed lines) between the polymeric chains: (a) viewed in the direction [010], (b) in the direction [100].

Fig. 8
Fig. 8 Crystal packing of 6 showing hydrogen bonding N-H/O (dashed lines) between the polymeric chains and p-interactions between imidazole ligands.Chains A (C 2 -symmetric) and B (centrosymmetric) are marked.

Table 5 g
-tensor parameters used in the simulations and exchange interaction parameter, |J|, obtain by linewidth analysis.The values of R parameters, defined by eqn (3) is also presented

Table 6
The shortest Cu/Cu intra-and interchain distances for studied compounds 1-6