Journal of Molecular Structure 981 (2010) 4045

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Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Syntheses, X-ray crystal structure and magnetic studies of a new dinuclear CuII complex, [Cu2(l-Cl)2L2Cl2]2CH3CN, L: N,N,N0 ,N0 -tetraisopropylpyridine2,6-dicarboxamide
Pratibha Kapoor a,*, Ajay Pal Singh Pannu b, Mukesh Sharma a, Maninder Singh Hundal b,*, Ramesh Kapoor c, Montserrat Corbella d,*, Nria Aliaga-Alcalde d,e,1,*
a

Department of Chemistry, Panjab University, Chandigarh 160 014, India Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, India c Department of Chemistry, Indian Institute of Science Education and Research, Mohali, Chandigarh 160 019, India d Department de Qumica Inorgnica, Universitat de Barcelona (UB), Mart i Franqus 1-11, 08028 Barcelona, Spain e ICREA: Instituci Catalana de Recerca i Estudis Avanats, Universitat de Barcelona (UB), Spain
b

a r t i c l e

i n f o

a b s t r a c t
Reaction of anhydrous copper(II) chloride with N,N,N0 ,N0 -tetraisopropylpyridine-2,6-dicarboxamide (L) leads to the synthesis of [Cu2Cl4L2]2CH3CN, 1. The ligand coordinates to each CuII ion in a bidentate fashion through pyridine nitrogen and only one of the carbonyl oxygen atoms of the amide group rather than using tridentate coordination mode ONO. The structure can be described as a dichloro bridged centrosymmetric dimer where the two copper centers are pentacoordinated in a square pyramidal fashion. The two pyramids are arranged sharing a basal edge with their apical positions oriented opposite to each other. The crystal packing investigations show a 2D sheet in the lattice held together by dimeric acetonitrile entities. Complex 1 shows weak antiferromagnetic coupled Cu2+ ions. 2010 Elsevier B.V. All rights reserved.

Article history: Received 27 May 2010 Received in revised form 14 July 2010 Accepted 14 July 2010 Available online 21 July 2010 Keywords: N,N,N0 ,N0 -tetraisopropylpyridine-2,6dicarboxamide X-ray crystal structure Pentacoordinated Magnetic studies Antiferromagnetic

1. Introduction Over the last few decades dinuclear CuII complexes with Cu (l-X)2Cu (X = OH, OR, Cl) core have been extensively studied to provide further understanding on the structural and chemical factors which govern the magnetic interactions between the metal centers involved [16]. It has been found that the complexes that contain l-OH bridges (having structural similarities) exhibit comparable magneto-structural correlations [513] while those with l-OR bridges differ in geometries and thus, their bond lengths and angles have to be taken into account while describing magneto-structural correlations [1420]. The dinuclear CuII complexes with Cu(l-Cl)2Cu core occupy prime importance [14,2125]; this class of dinuclear compounds show a variety of different structures ranging from square pyramid to trigonal bipyramid with diverse bond distances (CuCl) and angles (CuClCu) depending on the coordinated ligands and counterions thus, requiring a specic study for each case.

It is well known that the incorporation of pyridine-based ligands have lead to construction of supramolecular frameworks leading to molecular-based magnets [2629]. The weak forces such as hydrogen bonding, van der Waals forces, pp interactions and dipoledipole interactions are very common in the creation of these types of systems [3033]. Several copper complexes containing pyridine based multidentate ligands and halogen-bridges have been studied to conclude meaningful magneto-structural correlations for these systems [2633]. Therefore, in order to develop a correlation between molecular structure and magnetic behaviour and to investigate the crystal structure interactions leading to supramolecular framework expansion among such systems, we have extended our work involving pyridine-based ligands like N,N,N0 ,N0 -tetraalkylpyridine-2,6-dicarboxamides and derivatives [3439] to report the synthesis, structure, and magnetic properties of a new dinuclear CuII complex, [Cu2(l-Cl)2L2Cl2]2CH3CN, 1. 2. Experimental

* Corresponding authors. E-mail addresses: pkapoor@pu.ac.in (P. Kapoor), mshundal.chem@gndu.ac.in (M.S. Hundal), montse.corbella@qi.ub.es (M. Corbella), nuria.aliaga@qi.ub.es (N. Aliaga-Alcalde). 1 ICREA Junior Researcher. 0022-2860/$ - see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2010.07.021

2.1. Materials All reactions were carried out in anhydrous solvents under dry N2 atmosphere. Solvents and other reagents were dried using

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standard techniques as described [40]. Anhydrous copper chloride was prepared by reuxing hydrated copper(II) chloride with thionyl chloride. The anhydrous product was ltered, washed with toluene and dried in vacuo. 2.2. Syntheses The ligand (L) was prepared as per the method described earlier [41]. The IR spectrum of the ligand shows peaks at: (cm1) 1645s (tCO), 1575m, 1550m, 1456m, 1020m, 779m, 755w, 660w, 630m, 579m, 430w. 2.2.1. Preparation of complex (1) A solution of anhydrous CuCl2 (1.20 g, 9.0 mmol) in acetonitrile was added to a solution of ligand (L) (6 g, 18.0 mmol) in CH3CN. After stirring for 34 h the solid yellowish green product (3.18 g, 70%) was separated by ltration and dried in vacuo. Even when the metal salt and ligand were added in 1:1 M ratio same product was obtained. [Cu2Cl4L2]2CH3CN, 1: Anal. Found: C, 49.34; H, 6.69; N, 10.86%. Calc. for C42H68Cu2N8O4Cl4: C, 49.56; H, 6.73; N, 11.01%. M.p.: 134 C. Molar conductance (X1 cm2 mol1): 40.5 (CH3CN). IR: tCO 1576 cm1. 2.3. Physical measurements Elemental analyses (C, H, N) were performed on a PerkinElmer model 2400 CHN analyzer. IR spectra were recorded as KBr pellets on a PerkinElmer RX-1 FTIR spectrophotometer. Thermal analysis was carried out on a Shimadzu-DTG 60 analyser under dry N2 atmosphere. UVvis spectrum was recorded on Shimadzu Pharmaspec UV-1700 spectrophotometer in CH3OH. Molar conductance of millimolar solution of the complex was measured at 25 C on a conductivity bridgeDigital Conductivity Meter CC 601. Magnetic susceptibility measurements between 2300 K and magnetization measurements, at 2 K, between 0 and 5 T, were carried out in a SQUID Quantum Design Magnetometer, model MPMP at the Unitat de Mesures Magntiques (Universitat de Barcelona) on polycrystalline samples (30 mg). 2.4. X-ray crystallography Crystallization of complex 1 by very slow evaporation from its saturated solution in CH3CN at room temperature yielded suitable light green colored single crystals for X-ray analysis. The data were collected at 298 K on a Siemens P4 Single crystal X-ray diffractometer using the XSCANS package [42]. The data were collected by the h2h scan mode with a variable scan speed up to a maximum of 2h = 60 using graphite monochromatised Mo Ka radiations (k = 0.71073 ). To monitor the stability of the crystal 3 standard reections were measured after every 97 reections. The data were corrected for Lorentz and polarization effects. The structure was solved by direct methods using SIR97 [43] and rened by full-matrix least-squares renement techniques on F2 using SHELXS-97 [44] in the WINGX package [45] of programs. All atoms were rened anisotropically. All hydrogen atoms were attached geometrically riding on their respective carrier atoms with Uiso being 1.5, 1.2 and 1.2 times the Uiso of their carrier methyl, methylene and aromatic carbon atoms, respectively. A summary of crystal data, experimental and renement details is given in Table 1. 3. Results and discussion 3.1. IR and absorption spectra The N,N,N0 ,N0 -tetraalkylpyridine-2,6-dicarboxamide ligands usually coordinate to metal ions in a tridentate fashion through

Table 1 Crystal data and structure renement for complex 1. Sum formula Formula weight Temperature Wavelength Crystal system, space group Unit cell dimensions C42H68Cl4Cu2N8O4 1017.94 293(2) K 0.71069 Monoclinic, P21/c a = 12.898(3) , a = 90 b = 13.773(5) , b = 102.550(5) c = 14.795(4) , c = 90 2565.4(13) 3 2, 1.318 Mg/m3 1.082 mm1 1068 0.20 0.18 0.18 mm 1.6225.50 0 6 h 6 15, 0 6 k 6 16, 17 6 l 6 17 5003/4784 [R(int) = 0.0362] 100.0% 0.8290 and 0.8126 Full-matrix least-squares on F2 4784/0/271 0.865 R1 = 0.0434, wR2 = 0.0975 R1 = 0.0979, wR2 = 0.1409 0.508 and 0.707 e A3

Volume Z, Calculated density Absorption coefcient F(0 0 0) Crystal size Theta range for data collection Limiting indices Reections collected/unique Completeness to theta = 25.50 Max. and min. transmission Renement method Data/restraints/parameters Goodness-of-t on F2 Final R indices [I > 2sigma(I)] R indices (all data) Largest diff. peak and hole

pyridine ring nitrogen and carbonyl oxygen atoms [3439,41]. However, in the present case, owing to the formation of dimeric structure, the steric requirements of the ligand forces a bidentate mode of coordination to the metal ion, using the pyridine nitrogen and only one of the carbonyl oxygen atoms. This is clearly observed in the IR data where a carbonyl stretching frequency appears at 1576 cm1 suggesting carbonyl coordination to copper center while the other tCO band at 1650 cm1 is attributed to the free carbonyl group as in the ligand. The higher energy shift of the pyridine ring vibrations (1585, 1560, 1465, 1440, 1035, 670 and 435 cm1) gives a clear indication of the participation of this fragment through the nitrogen atom which is coordinated to the copper center. The absorption spectrum of a polycrystalline sample of the complex [Cu2Cl4L2]2CH3CN, 1 is shown in Fig. 1. The sharp bands between 250 and 290 nm (40,00034,482 cm1) range may correspond to the ligand-centered pp or np transitions and a band at 462 nm (21,640 cm1, e = 1412 l mol1 cm1) may correspond to the ligand-to-metal charge transfer transition(s). A broad band envelope corresponding to dd transition(s) is observed in the complex 1 (CuCl3NO chromophore) with a maxima around 872 nm (11,500 cm1, e = 223 l mol1 cm1) indicating distorted square-pyramidal geometry. This spectrum is characteristic of distorted Cu(II) complexes where the bands arise from the dxz(dyz) ? dx2y2 and dxy ? dx2y2 transitions. The high extinction coefcient associated with the dd transition(s) is indicative of

Fig. 1. Absorption spectrum of 1.

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low-symmetry ve-coordinate CuII complexes. A few CuII complexes with square-pyramidal geometry are listed in (Supplementary Information Table S1) with their absorption spectra [46]. 3.2. Thermal studies Thermogravimetric analysis (TGA) data of 1 as a function of temperature up to 800 C (solid line). The negative of the rst derivative is also plotted as a function of temperature (broken line). The thermogravimetric analysis performed on 1 is shown in Fig. 2. The percentage weight loss observed (% TGA) along with the negative values of the rst derivative are plotted as functions of temperature between 100 and 800 C. The curves show threestep weight loss upon heating to 800 C with simultaneous weight loss of inorganic and organic fragments. The residue after heating above 750 C corresponds to the formation of metallic copper. Initially, it undergoes a slow weight loss on heating above room temperature due to the loss of solvent of crystallization (CH3CN) which continues up to about 200 C. Above this temperature it undergoes a sudden weight loss due to the complete breakdown of the complex with the loss of CuCl2L2. The decomposition scheme is suggested based on the observed weight loss. Calculated weight loss values are provided in parentheses.

Cu2 Cl4 L2 2CH3 CN ! Cu2 Cl4 L2 2CH3 CN; wt: loss 7:88:1% Cu2 Cl4 L2 ! CuCl2 CuCl2 L2 ; wt: loss 78:778:8% CuCl2 ! Cu Cl2 ; wt: loss 7:27:0%
3.3. Molecular and crystal structures of 1 The structure of complex 1 was determined using single crystal X-ray crystallography (Fig. 3). It consists of a centrosymmetric dimer in which each CuII ion is pentacoordinated. The ligand N,N,N0 ,N0 tetraisopropylpyridine-2,6-dicarboxamide (L) coordinates to each CuII ion in a bidentate fashion through pyridine nitrogen N1 and one of the carbonyl oxygen atoms O1 with CuN1 = 2.025(4) and CuO1 = 2.444(2) . The second carbonyl oxygen atom O2 moves away from the copper center probably due to the steric requirements of the ligand thereby extending the Cu1O2 distance to 2.911(3) beyond any bonding range between them. The amide groups C1C13O2N3 and C5C6O1N2 are twisted through 35.2(1) and 49.5(1) with respect to the pyridine plane in the opposite

Fig. 2. Thermogravimetric analysis (TGA) data of 1 as a function of temperature up to 800 C (solid line). The negative of the rst derivative is also plotted as a function of temperature (broken line).

directions to facilitate maximum coordination to the metal ion without much strain in the structure. Both the CuII ions are linked to each other through two bridging chloro groups, Cl1 and its symmetry equivalent Cl1i (where i = x, y, z), thus suggesting a square planar arrangement for the Cu(l-Cl2)Cu core. The bridging is slightly unsymmetrical in nature with CuCl1 = 2.335(3) and CuCl1i = 2.297(2) . The fth coordination site around each copper is occupied by a terminal chloride atom Cl2 with Cu1Cl2 distance being 2.215(1) . The Cu Cu nonbonding distance within the complex is 3.424(3) . It is generally observed that most of the ve-coordinated complexes have neither an ideal trigonal bipyramidal (tbp) nor square pyramidal (sp) environment but their geometry is generally intermediate between the two extremes. Addison and co-workers have suggested a parameter s as a measure of extent of distorsion from the ideal geometry [47]. The parameter s is determined by the relation s = (b a)/60 (where a and b are the larger basal angles with b > a) and its value may vary from 0, representing ideal sp to 1, denoting ideal tbp geometry. In complex 1, the local arrangement for each copper center indicates a distorted square-pyramidal geometry with s = 0.36. The pyridine nitrogen atom N1, terminal chloride ion Cl2 along with the two bridging chloride ion Cl1 and Cl1i form the basal plane in the square pyramid while the apical position is occupied by the coordinating carbonyl oxygen atom O1. The bond lengths and bond angles for complex 1 are listed in Table 2. A similar CuII complex [Cu(ppmma)Cl2] [48] [where ppmma = phenyl-N-[(pyridine-2-yl)methylene] methaneamide] also contains Cu(l-Cl2)Cu core with each CuII atom occupying squarepyramidal geometry. The Cu Cu nonbonding distance of 3.5103(7) is comparable to the one observed in the present complex. The Cu(l-Cl2)Cu unit is planar with a crystallographic inversion center. The two unequal central CuCl bond distances in the bridged Cu2Cl2 unit are 2.2613(7) and 2.6957(8) , which shows high degree of unsymmetrical bridging as compared to the present complex. In the present complex the bridging is slightly unsymmetrical in nature with CuCl1 = 2.335(3) and CuCl1i = 2.297(2) . Another centrosymmetric CuII complex with similar Cu(l-Cl2)Cu core is [Cu (dmamhp)Cl2]2 [where dmamhp = 2-dimethylaminomethyl-3-hydroxypyridine] [49]. The CuClCu bridge is formed by atoms Cu, Cl2, Cl2i and Cui. The CuCl distances in the bridging unit are 2.298(2) and 2.639(2) again showing the unsymmetrical bridging of high degree as compared to the present complex. The three types of congurations adopted by dinuclear dihalobridged CuII complexes with square-pyramidal environment which have been experimentally characterized are: (a) square pyramids sharing one base-to-apex edge but with parallel basal planes [5052], (b) square pyramids sharing one base-to-apex edge with the two bases nearly perpendicular to one another [4] and (c) square pyramids share a basal edge having coplanar basal planes with their apices in opposite directions [5356]. Owing to the steric bulk (isopropyl groups) on the amide side arms of the ligand and the formation of the dinuclear entity, one coordinating carbonyl oxygen atom coordinates to metal center from above the Cu(l-Cl)2Cu core plane while the other coordinates from below this plane. The orientation of the two neighboring square pyramids thus obtained is upside down with respect to each other. Therefore, this structure belongs to the class (c) of dimeric CuII complexes (Fig. 4). The structure is stabilized by intra and intermolecular hydrogen bonding. There is a strong intramolecular H-bonding between the amide oxygens O1, O2 and the hydrogen atoms of the propyl groups attached to the amide nitrogens. These four intramolecular H-bonding interactions, C8H8B O1 (2.363(3) ), C9H9C O1 (2.448(3) ), C18H18B O2 (2.524(2) ) and C19H19C O2 (2.394(4) ) twist the propyl groups towards the amide oxygens O1 and O2 (Fig. S1 Supplementary Information).

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C9 C7 C12 N2 C20 C4 C21 C3 N4 C2 C1 C14 C13 C15 C16 N3 O2 N1 Cu1 Cl2 Cl1 C5 C6 O1 C10 C11 C8

C17 C18 C19

Fig. 3. The ORTEP diagram and the atom numbering scheme used in the structure analysis of complex 1 with 50% ellipsoidal probability.

Table 2 Important bond lengths [] and bond angles [] for complex 1. N(1)Cu(1) O1Cu1 Cl(1)Cu(1) Cl(1)Cu(1)a Cl(2)Cu(1) Cu(1)Cl(1)a C(1)N(1)Cu(1) C(5)N(1)Cu(1) Cu(1)Cl(1)Cu(1)a N(1)Cu(1)Cl(2) N(1)Cu(1)Cl(1) Cl(2)Cu(1)Cl(1) N(1)Cu(1)Cl(1)a Cl(2)Cu(1)Cl(1)a Cl(1)Cu(1)Cl(1)a
a

2.025(4) 2.444(2) 2.297(2) 2.335(2) 2.214(2) 2.335(2) 123.2(3) 116.7(3) 95.3(5) 94.3(1) 169.1(1) 93.8(6) 88.5(2) 169.0 84.6(5)

Symmetry transformations used to generate equivalent atoms: a = x + 1, y, z + 1.

Fig. 4. The two edge sharing square pyramids with their apical positions upside down with respect to each other in complex 1.

4. Magnetic properties Among the intermolecular H-bonding interactions, the chloride ion Cl1 is donor to C3H3 Cl2i (2.926(2) ) interaction while the chloride ion Cl(2) is involved in C16H16A Cl2i 2.878(2) and C2H2 Cl2i (2.923(3) ) interactions (where i = x, y + 1/2, +z + 1/2). Furthermore, the C20H20B N4ii (2.741(1) , ii = x + 1, +y + 1/2, z + 1) hydrogen bonding interaction between the acetonitrile (solvent) molecules leads to the formation of H-bonded solvent dimers. These dimers are involved in hydrogen bonding with the complex molecules (C14H14 N4iii (2.742(3) , and C20H20A O1iii where iii = x + 1, y + 1, z + 1,) leading to the formation of a 2D sheet thus stabilizing the entire crystal lattice (Fig. 5). Solid-state, variable-temperature (5300 K) magnetic susceptibility data using a 1.0 T eld were collected on polycrystalline samples of compound 1. The data for compound 1 shows (Fig. 6) a behaviour characteristic of very weak, antiferromagnetic coupled Cu2+ ions. The vMT value at 300 K is 0.88 cm3 mol1 K, higher than that expected for two uncoupled S = 1/2 spins assuming g = 2.0 (0.75 cm3 mol1 K) and it does slowly decrease upon cooling until approximately 50 K, dropping faster then and arriving nally to 0.56 cm3 mol1 K at 5 K (Fig. 6). The experimental magnetic data were tted using a derived equation of BleaneyBower [57] for dinuclear CuII complexes with

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Fig. 5. The crystal packing diagram showing the intermolecular hydrogen bonding interactions. The solvent dimers (ball and stick mode) hold the crystal lattice together. The hydrogen atoms of the complex (other than those involved in hydrogen bonding) are omitted for clarity.

the Hamiltonian in the form H = JS1 S2. The best t parameters were found for J = 3.72 0.04 cm1, g = 2.09 0.01, TIP = 180 106 cm3 mol1 and a nal R = 8 105. In principle, a coupling between two pentacoordinated Cu atoms through chloro bridges is expected to be weaker than those observed in analogous systems with oxo or hydroxo ligands. CuCl distances are larger and basically, this reduces the efciency of the coupling [4]. Hence, the larger the distance, the smaller the exchange. Also, the strength and sign of the exchange depends on (i) the geometry and arrangement among the copper centers: coplanar, parallel or perpendicular; (ii) the CuClCu angle, where at values close to 90 accidental orthogonality is observed and also (iii) on the distortions between square pyramidal (sp) and trigonal bipyramidal (tbp) arrangements [4,47]. The bifold angle, r, provides more insight on the nal magnetic properties too. This is

0.90 0.85

MT / cm mol K

-1

0.80 0.75 0.70 0.65 0.60 0.55 0 50 100 150 200 250 300

the angle formed by two planes: the plane that contains the copper centers and the basal ligands on the core, Cu2Cl2, and the lateral plane dened by Cu1, N1, Cl2 and Cl1 atoms {Fig. S2 (Supplementary Information)}[58]. In compound 1, the single electron on each Cu atom is mostly of the dx2 y2 type (basal) and consequently, the interaction between the magnetic orbitals of the two coppers atoms will occur through the central Cl ions [58]. In general, when CuCl distances reach 2.8 the two paramagnetic orbitals are nearly degenerate and the coupling is ferromagnetic. For 1, CuCl distances are close to 2.3 , being shorter than the average found for similar compounds [58]. In addition, CuClCu and r angles are 95.3 and 13.84, respectively. The observed J value for this compound corresponds to a weak antiferromagnetic coupling that could be explained as the sum and contribution of the parameters/factors described above. This way, having a CuClCu angle higher than 90 will increase the energy differences between the magnetic orbitals making antiferromagnetic interactions possible. In the past, it was already established that ferromagnetic exchange interactions increase as the bifold angle increases. Here, complex 1 exhibits a rather small value of r, which also supports the antiferromagnetic interaction observed. All together this information matches well with the nal J value found for 1. 5. Conclusions By employing pyridine-2,6-dicarboxylic acid based ligand N,N,N0 N0 -tetraisopropylpyridine-2,6-dicarboxamide (L) we have synthesized a new dinuclear CuII complex with Cu(l-Cl)2Cu core. The ligand do not follow the usual tridentate coordination mode (using ONO donor atoms) as expected but coordinates to metal ion in bidentate fashion using pyridine nitrogen and only one of the carbonyl groups. The existence of intra and intermolecular Hbonding interactions involving the solvent molecules play an important role in the creation of supramolecular architectures. The thermal studies performed on 1 show the stability of its molecular structure as the breakdown of the complex starts only above 200 C. In addition, magnetic studies performed on 1 show very

Temperature / K
Fig. 6. Fitting of the vMT vs. T of compound 1 between 5.0 and 300.0 K. The experimental data is shown as black spheres and the red line corresponds to the theoretical values. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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weak, antiferromagnetic coupling within the Cu2+ ions of each cluster. This feature agrees well with the magnetic behaviour expected by such type of clusters reported earlier (with two square pyramids sharing a basal edge having coplanar basal planes and their apices in opposite directions) in cognizance with CuCu distances, CuClCu angles, s and the bifold angle. Altogether, complex 1 is a new addition to the family of Cu (l-Cl)2Cu compounds with the introduction of the N,N,N0 ,N0 tetraisopropylpyridine-2,6-dicarboxamide as a bidentate ligand exhibiting weak antiferromagnetic interactions due to its structural pattern. Acknowledgements Ajay Pal Singh Pannu thanks UGCSAP for research fellowship. Dr. Pratibha Kapoor thanks CSIR, New Delhi for nancial support. The Spanish authors thank the Ministerio de Educacin y Ciencia (CTQ2009-07264/BQU and CTQ2009-06959/BQU), the Comissi Interdepartamental de Recerca i Innovaci Tecnolgica de la Generalitat de Catalunya (CIRIT) (2009SGR1454) and ICREA (Instituci Catalana de Recerca i Estudis Avanats) for the nancial support. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.molstruc.2010.07.021. References
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