Dicopper(II) Metallacyclophanes with N,Nâ²-2,6-Pyridinebis(oxamate

Article pubs.acs.org/IC

Dicopper(II) Metallacyclophanes with N,N′‑2,6-Pyridinebis(oxamate): Solution Study, Synthesis, Crystal Structures, and Magnetic Properties Tamires S. Fernandes,† Ramon S. Vilela,† Ana K. Valdo,† Felipe T. Martins,*,† Enrique García-España,‡ Mario Inclán,‡ Joan Cano,‡,# Francesc Lloret,‡ Miguel Julve,*,‡ Humberto O. Stumpf,& and Danielle Cangussu*,† †

Universidade Federal de Goiás, Instituto de Química, Campus Samambaia, CP 131, CEP 74001-970 Goiânia, GO Brazil Departament de Química Inorgànica/Instituto de Ciencia Molecular (ICMol), Facultat de Química de la Universitat de València, C/Catedrático José Beltrán 2, 46980 Paterna (València), Spain # Fundació General de la Universitat de València (FGUV), Universitat de València, València, Spain & Departamento de Química, ICEx, Universidade Federal de Minas Gerais, Minas Gerais 31270-901, Brazil ‡

S Supporting Information *

ABSTRACT: The complexing ability of copper(II) in solution by the ligand N,N′-2,6-pyridinebis(oxamic acid) (H4mpyba, H4L) was determined through potentiometric and UV−vis spectroscopy at 25 °C and 0.15 M NaCl. The logarithms of the equilibrium constants for its copper(II) complexes according to the eqs 2H2L + 2Cu ⇆ [Cu2(H2L)2], 2H2L + 2Cu ⇆ [Cu2(H2L) (HL)] + H, 2H2L + 2Cu ⇆ [Cu2(HL)2] + 2H, 2H2L + 2Cu ⇆ [Cu2(HL)(L)] + 3H, and 2H2L + 2Cu ⇆ [Cu2L2] + 4H were 12.02(7), 8.04(5), 1.26(6), −7.51(6), and −16.36(6), respectively. The knowledge of the solution behavior has supported the synthesis of three new compounds bearing the common building block Cu 2L 24−. Their formulas are (Me4N)4[Cu2(mpyba)2(H2O)2]·H2O (1), (Me4N)4[K2Na2Cu4(mpyba)4(H2O)6.8]·1.6H2O (2), and [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3) (Me4N+ = tetramethylammonium cation). The [Cu2(mpyba)2(H2O)2]4− tetraanionic unit, which is present in 1, has a [3,3] metallacyclophane-type motif connected by two N−Cu−N bonds. In 2, a heterotrimetallic decanuclear nanocage is formed through front-to-front assembly of two [Cu2(mpyba)2]4− units, which also coordinate to potassium(I) and sodium(I) cations by means of carboxylate oxygens from oxamate. The structure of 3 consists of heterobimetallic layers of formula [Na6Cu2(mpyba)2Cl2(H2O)8] and crystallization water molecules, which are interlinked by hydrogen bonds leading to a supramolecular three-dimensional network. The investigation of the magnetic properties of 1−3 in the temperature range 1.9− 300 K shows the occurrence of ferromagnetic interactions between the dicopper(II) metallacyclophane unit [J = +6.85 (1), +7.40 (2), and +7.90 cm−1 (3); H = −JSCu1·SCu2, where SCu1 = SCu2 = 1/2]. Theoretical calculations on 1−3 were carried to substantiate the nature and magnitude of the involved magnetic interactions and to support the occurrence of a spin polarization mechanism accounting for them.

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of better control.9 This is the case for helices,10 grids,11 and ladders,12 among others. These frameworks can be obtained through different synthetic approaches, including the direct use of multidentate ligands coordinating to different transition metal ions in one-pot reaction medium13 or the construction of discrete metalloligands to be reacted in a next synthetic step with a second metal ion and even with additional ligands.7,8a,14 In this sense, heteronuclear coordination architectures with N-substituted aromatic oligo(oxamato) ligands are known, which is the synthetic strategy consisting of using stable

INTRODUCTION

The construction of coordination cages has attracted significant attention in recent years.1 Aside from understanding host− guest phenomena, their use in gas adsorption,2 drug delivery,3 catalysis,4 magnetic materials,5 molecular flasks,6 and protection of photosensitive guests against UV radiation1j,7 has also been demonstrated. Although a great number of examples of coordination cages can be found in the literature, only a reduced number of them concern oligo- and heteronuclear assemblies.5b,8 Such examples are still rare taking into account that their syntheses occur in one step.8a Although these metallomacrocycles are hard to prepare, the building of other heteronuclear coordination architectures has been the subject © XXXX American Chemical Society

Received: December 3, 2015

A

DOI: 10.1021/acs.inorgchem.5b02786 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry

thylammonium cation), which were magnetostructurally characterized. Ferromagnetic interactions between the copper(II) ions through the meta-substituted pyridyl fragment were observed in 1−3 for the first time, and their nature and magnitude were substantiated by DFT-type calculations. Remarkably, complex 2 exhibits the unprecedented assembly of two dicopper(II) metallacyclophanes linked by potassium(I) and sodium(I) cations in a front-to-front fashion as joined hemispheres to give rise to a coordination-based decanuclear nanocage.

dinuclear complexes as metalloligands toward different metal ions (Scheme 1). The complex formation between the anionic Scheme 1. Bis(N,N′-substituted oxamato)dicopper(II) as Metalloligand

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EXPERIMENTAL SECTION

General Information. All reactions were carried out under aerobic conditions. Chemicals and solvents were purchased from commercial sources and used as received. In the literature was reported a method of synthesis of the diethyl ester derivative of 2,6-diaminopyridine (Et2H2mpyba).20a In this work, Et2H2mpyba was prepared by a different method described for these types of ligands as follows.20b,c The details and characterization are available in the Supporting Information. K2H2mpyba·1.5H2O was prepared by treatment of the Et2H2mpyba proligand with aqueous KOH (1:2.1 proligand to base molar ratio) at 65 °C for 30 min under vigorous stirring. The potassium salt was obtained as a white solid after reducing the volume of the resulting solution under gentle heating. The precipitate was collected by filtration, washed with small amounts of cold water, and air-dried. Elemental analysis (C, H, N), IR, and NMR were conducted by the Microanalytical Service of the Federal University of Goiás. Values of 2:1:1 and 1:3:1 molar ratios for Cu:K:Na (2) and Cu:Na:Cl (3), respectively, were determined by electron probe X-ray microanalysis using a Philips XL-30 scanning electron microscope (SEM) from the Servicio Central de Soporte a la Investigación Experimental (SCSIE) at the Universitat de València. Synthesis of (Me4N)4[Cu2(mpyba)2(H2O)2]·H2O (1). A methanolic solution of Me4NOH 25% (2.05 mL, 5.07 mmol) was poured into an aqueous suspension of the Et2H2mpyba proligand (0.195 g, 0.63 mmol). An aqueous solution of CuCl2·2H2O (0.107 g, 0.63 mmol) was added dropwise under stirring, and the resulting solution was allowed to evaporate in a hood at room temperature. X-ray quality green needles of 1 grew after 3 days. They were collected by filtration, washed with a small amount of cold water, and dried over filter paper. Yield of ∼47%. Anal. Calcd for C34H60Cu2N10O15 (1): C, 41.84; H, 6.20; N, 14.35. Found: C, 41.54; H, 6.11; N, 14.23%. IR (KBr/cm−1): 3453 s [ν(O−H)] and 1692 s and 1627 s [ν(C = O)]. UV−vis (water) (λmax): 14947.7 cm−1. Synthesis of (Me4N)4[K2Na2Cu4(mpyba)4(H2O)6.8]·1.6H2O (2). A methanolic solution of Me4NOH 25% (1.06 mL, 2.52 mmol) was poured into an aqueous suspension of Et2H2mpyba (0.195 g, 0.63 mmol). Then, an aqueous solution containing CuCl2·2H2O (0.107g, 0.63 mmol), NaCl (0.019 g, 0.32 mmol), and KCl (0.024 g, 0.32 mmol) was added dropwise under continuous stirring, and the resulting green solution was placed in a hood to evaporate slowly at room temperature. Green prisms of 2 were grown after 4 days. Yield of ∼69%. Anal. Calcd for C52H76.8Cu4N16O32.4K2Na2 (2): C, 34,26; H, 4.25; N, 12.29. Found: C, 35.50; H, 4,07; N, 12.34%. IR (KBr/cm−1): 3446 s [ν(O−H)] and 1690 s, 1659 s and 1621 s [ν(C = O)]. UV−vis (water) (λmax): 15772.8 cm−1. Synthesis of [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3). A solution of NaOH (0.113 g, 2.83 mmol) was poured into an aqueous suspension of Et2H2mpyba (0.195 g, 0.63 mmol). Then, an aqueous solution of CuCl2·2H2O (0.107 g, 0.63 mmol) was added dropwise under continuous stirring, and the resulting solution was allowed to evaporate at room temperature. X-ray quality green plates of 3 grew after 2 days. Yield of ∼90%. Anal. Calcd for C18H36Cu2N6O27Na6Cl2 (3): C, 19.54; H, 3.25; N, 7.60. Found: C, 19.61 H, 3.19; N, 7.65%. IR (KBr/cm−1): 3435 s [ν(O−H)] and 1638 s and 1592 s [ν(C = O)]. UV−vis (water) (λmax): 15600.6 cm−1. Physical Measurements. Infrared and electronic spectra of the complexes 1−3 were recorded with a PerkinElmer Precesily Spectrum

double-stranded dicopper(II) complex [Cu2(mpba)2]4− [mpba = N,N′-1,3-phenylenebis(oxamate)] and M2+ ions (M = Mn and Co) yields metallacyclophane-based Mn(II)Cu(II) brickwall layers with a (6,3) net topology where the [Cu2(mpba)2]4− metalloligand adopts a tetrakis(bidentate) coordination mode.15 The versatility of this type of ligand makes it an excellent candidate to be used in coordination chemistry. This quality is due to its inherent ability to bind to different transition metal ions and distinct output properties of the designed materials, such as molecular magnets.16 In addition, many types of coordination environments can be assembled with these oxamate-based ligands, for instance, the dimetallacyclophanes used as dynamic porous magnets for magnetic sensing and as magnetic sensors of the “host−guest” type for drug delivery.17 Most of the studies on these compounds were made in the solid state. In the coordination chemistry field context, some examples show that solution studies are important to direct the synthesis of the desired compounds to support the results obtained from the solid-state works and to establish the relationships between them with properties in solution.18,19 Solution studies have minimally been exploited for compounds containing oxamate-based ligands. Here, we focus on the preparation of complexes with the N,N′-2,6-pyridinebis(oxamate) ligand (the fully deprotonated form of H4mpyba) (see Scheme 2) and copper(II) ions both in Scheme 2. Structural Formula of H4mpyba

solution and in the solid state. On the basis of the knowledge of the complexing ability in solution, it was possible to prepare the complex in its tetra-anionic form, Cu2L24−, and further to isolate three complexes of formula (Me4N)4[Cu2(mpyba)2(H2O)2]·H2O (1), (Me 4 N) 4 [K 2 Na 2 Cu 4 (mpyba) 4 (H 2 O) 6.8 ]·1.6H 2 O (2), and [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3) (Me4N+ = tetrameB


Article

Inorganic Chemistry Table 1. Crystal Data and Refinement Statistics for Complexes 1−3 structural formula in asymmetric unit Fw (g/mol) cryst dimensions (mm3) cryst syst space group Z/Z′ T (K) unit cell dimensions

V (Å3) ρcalc (mg/m3) absorption coefficient μ (mm−1) θ range for data collection (deg) index ranges

data collected unique reflections symmetry factor (Rint) completeness to θmax (%) F (000) refined parameters goodness-of-fit on F2 (S)a final R1b factor [ I > 2σ(I)] wR2c factor (all data) largest diff. peak/hole (eÅ−3)

1

2

3

[N(CH3)4]2Cu (C9H3N3O6)(H2O)2 497.02 0.27 × 0.10 × 0.09 monoclinic C2/c 8/1 296(2) 22.407(3) 15.961(2) 16.0589(18) 116.624(2) 5134.4(11) 1.286 0.896 5.91−27.08 −28 ≤ h ≤ 23 −20 ≤ k ≤ 19 −6 ≤ l ≤ 19 11576 5344 0.0299 94.5 2088 322 1.302 0.0938 0.3389 1.273/−0.450

[N(CH3)4]CuK0.5Na0.5 (C9H3N3O6)(H2O)2.1 455.72 0.25 × 0.18x 0.05 orthorhombic Cmca 16/1 296(2) 22.521(18) 13.220(18) 24.87(3) 90 7406(14) 1.635 1.354 1.96−25.62 −22 ≤ h ≤ 22 −15 ≤ k ≤ 11 −30 ≤ l ≤ 17 9766 3534 0.0591 98.5 3744 269 1.017 0.0528 0.1306 0.855/−0.492

CuNa3Cl (C9H3N3O6)(H2O)7.5 552.24 0.36 × 0.14 × 0.13 orthorhombic Pbcm 8/1 296(2) 13.0966(8) 21.1127(13) 14.9035(8) 90 4120.9(4) 1.780 1.324 1.55−26.38 −16 ≤ h ≤ 16 −26 ≤ k ≤ 26 −11 ≤ l ≤ 18 43486 4383 0.0377 100 2240 301 1.036 0.0500 0.1459 0.762 /−1.085

⎡ ∑w (F(2hkl)obs − F(2hkl)calc) ⎤1/2 b ⎡ ∑whkl (F(2hkl)obs − F(2hkl)calc)2 ⎤1/2 ⎡ ∑ ||F(hkl)obs| − |F(hkl)calc|| ⎤ c R=⎢ S = ⎢ hkl |N − N | = wR ⎥ ⎢ ⎥ 2 ⎥ ∑ |F(hkl)obs| ∑w F(2hkl)obs ⎣ ⎦ r p ⎣ ⎦ ⎣ ⎦ hkl

a

400 FT-IR/FT-FIR spectrophotometer (as KBr pellets in the range 4000−400 cm−1) and a PerkinElmer UV/vis Lambda 45 spectrophotometer, respectively. Magnetic susceptibility measurements on crushed crystals of 1−3 were carried out on a Quantum Design SQUID magnetometer operating between 1.9 and 300 K under applied dc magnetic fields of 0.1 T (T ≥ 50 K) and 500 G (T < 50 K). The corrections for the diamagnetism of the constituent atoms were estimated from Pascal’s constants21 as −527 × 10−6 (1), −382 × 10−6 (2), and −482 × 10−6 cm3 mol−1 (3) [per two copper(II) ions]. Experimental susceptibilities were also corrected for the temperatureindependent paramagnetism [60 × 10−6 cm3 mol−1 per copper(II) ion] and the magnetization of the sample holder (a plastic bag). Electromotive Force Measurements and UV−Vis Titrations. The potentiometric titrations were carried out at 298.1 ± 0.1 K using 0.15 mol dm−3 NaCl as the supporting electrolyte. The experimental procedure (buret, potentiometer, cell, stirrer, micro- computer, etc.) has been fully described elsewhere.22 The acquisition of the EMF data was performed with the computer program PASAT.23 The reference electrode was an Ag/AgCl electrode in saturated KCl solution. The glass electrode was a calibrated hydrogen ion concentration probe by titration of previously standardized amounts of HCl with CO2-free NaOH solutions. The equivalence point was determined by the Gran’s method,24 which gives the standard potential, E°′, and the ion product obtained was 13.73(1) in pure water.25 The computer program HYPERQUAD was used to calculate the protonation and stability constants.26 The pH range investigated (pH = −log[H+]) was 2.0− 11.0. The different titration curves for each ligand were treated as separate curves without significant variations in the values of the stability constants. Finally, the sets of data were merged together and treated simultaneously to give the final stability constants. H2mpyba2− (noted H2L2−) and Cu(ClO4)2 solutions were prepared with 0.15 mol dm−3 NaCl. Absorption spectra were recorded on a

spectroscopy system using equimolecular mixtures of H4L and Cu(II) at 1.0 × 10−5 M. The pH values were measured with a pH meter, and adjustments of the hydrogen ion concentration of the solutions were made with diluted HCl and NaOH solutions. The computer program HypSpec was used to calculate the values of the stability constant from spectroscopic data.26 X-ray Crystallography. Well-shaped single crystals of 1−3 were selected for the X-ray diffraction data collection at room temperature. Mo Kα radiation from an IμS microsource with multilayer optics was used (Bruker-AXS Kappa Duo diffractometer with an APEX II CCD detector). The diffraction frames were recorded by φ and ω scans using APEX2,27 and raw data set treatment was performed using the program SAINT and SADABS.27 Multiscan absorption correction has been employed to both data sets.28 The structures were solved by direct methods with SHELXS-97,29 wherein C, O, N, Cu, Na, and K were readily assigned from the Fourier map. The initial models were refined by the full-matrix least-squares method on F2 with SHELXL97,29 adopting anisotropic thermal parameters for non-hydrogen atoms. Site occupancy factors (SOF) of the water oxygens found in the cage of 2 were set to either 25 (O3wa), 20 (O3wb), or 15% (O3wc). Before SOF constraints, these parameters were refined freely to find their value. Hydrogen atoms of the aromatic rings were stereochemically positioned and refined with fixed individual isotropic displacement parameters [Uiso(H) = 1.2Ueq(Csp2) or 1.5Ueq(Csp3 and O)] using a riding model with fixed C−H bond lengths of either 0.93 (aromatic) or 0.96 Å (methyl). The hydrogen atoms of the water molecules were identified in the Fourier map, but their fractional coordinates were fixed during the refinements because unsuitable bonding geometry was output after trial refinements set free their coordinates. The MERCURY30 and ORTEP-331 programs were used within the WinGX 31 software package to prepare artwork representations. Crystallographic data and refinement parameters of C


Article

Inorganic Chemistry 1−3 are summarized in Table 1. Selected bond lengths and angles of 1−3 are listed in Table S1, whereas the hydrogen bonds for the three compounds are grouped in Table S2. Crystallographic details are available in the Supporting Information in CIF format. CCDC numbers 1053438 (1), 1053437 (2), and 1053439 (3). Computational Details. DFT calculations were performed on the three experimental geometries of the centrosymmetric and noncentrosymmetric dicopper(II) fragments of compounds 1−3 (see Figure S3) through the Gaussian 09 package using the B3LYP functional,32 the quadratic convergence approach, and a guess function generated with the fragment tool of the same program.33 Triple-ζ and double-ζ all electron basis sets proposed by Ahlrichs et al. are employed for the metal and for the rest, respectively.34,35 The magnetic coupling states were obtained from the relative energies of the broken-symmetry (BS) singlet spin state from the high-spin state with parallel local spin moments. More details regarding the use of the broken-symmetry approach to evaluate the magnetic coupling constants can be found in the literature.36−39

Table 2. Cumulative Equilibrium Constants Determined at 298 K in 0.15 NaCl reactiona

log βb

H2L + 2H ⇆ H4L H2L + H ⇆ H3L 2H2L + 2Cu ⇆ Cu2(H2L)2 2H2L + 2Cu ⇆ Cu2(H2L) (HL) + H 2H2L + 2Cu ⇆ Cu2(HL)2 + 2H 2H2L + 2Cu ⇆ Cu2(HL)L + 3H 2H2L + 2Cu ⇆ Cu2L2 + 4H

5.62(2)c 3.69(1)d, 3.72(1)c 12.02(7)d 8.04(5) 1.26(6) −7.51(6) −16.36(6)d

a

Charges were omitted for clarity. bValues in parentheses correspond to the standard deviation in the last significant digit. cBy UV−vis titrations. dBy potentiometric titrations.

carboxylate groups could be identified by potentiometric titration in the explored pH range 2.0−11.0 [pKa2 = 3.69(2)]. For determining the protonation constant of the second carboxylate group, which would take place at a more acidic pH, a UV−vis pH titration of a 10−5 M ligand solution was performed in the pH range 5.0−1.0. At pH 5.0, the spectrum consists of two bands centered at 236 and 300 nm. When acid is added, these two bands decrease, and two new bands appear at 263 and 334 nm. Three distinct isosbestic points are observed at 248, 276, and 314 nm, indicating equilibrium between the different protonated species (Figure 1).

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RESULTS AND DISCUSSION Synthesis, Infrared, and Eletronic Spectra. The study of complex formation between the copper(II) ion and the bis(oxamate) mpyba4− ligand afforded three different compounds. Complex 1 was isolated as a tetramethylammonium salt by the reaction of copper(II) chloride and Et2H2mpyba [diethyl ester of the N,N′-2,6-pyridinebis(oxamic acid)] after deprotonation and hydrolysis with Me4NOH (8:1 base to proligand molar ratio) in a water−methanol solvent mixture. Compound 2 was isolated by following the synthetic procedure for 1 but using half the amount of base and adding stoichiometric amounts of sodium(I) and potassium(I) as chloride salts. Interestingly, these univalent alkaline cations act as connectors of the dicopper(II) metallacyclophane units to yield an unprecedented dodecanuclear nanocage (see below). Complex 3 was isolated by reaction of copper(II) chloride and the diethyl ester derivative of 2,6-diaminopyridine (Et2H2mpyba) after deprotonation and hydrolysis with NaOH (4:1 base to ligand molar ratio) in aqueous solution. The sodium cations in 3 act as connectors of dicopper(II) metallacyclophane units to provide a neutral two-dimensional network. The IR spectra of 1−3 have in common the shift of the carbonyl bands from 1722 and 1702 cm−1 in the IR spectrum of Et2H2mpyba to 1692 and 1627 cm−1 (1), 1690, 1659, and 1621 cm−1 (2), and 1638 and 1592 cm−1 (3) as well as the lack of the amide N−H stretching, which is located at 3404 and 3332 cm−1 for Et2H2mpyba. These spectroscopic features are consistent with the coordination of the copper(II) ion of both the amide nitrogen and carboxylate oxygen atoms of the fully deprotonated mpyba4− ligand. The presence of water in 1−3 is reflected by the occurrence of medium to strong intensity absorption peaks in the frequency range 3450−3435 cm−1 of their IR spectra. Electronic spectra of 1−3 exhibit broad weak bands centered at approximately 14947.7, 15772.8, and 15600.6 cm−1, respectively, which corresponds to the typical d−d transitions of a square-pyramidal Cu(II) ion, as earlier found in related dinuclear oxamate copper(II) complexes.20b Solution Study. The deprotonation of the N,N′-2,6pyridinebis(oxamic acid) (H4L) and its complex formation with copper(II) in aqueous solution were investigated by means of electromotive force measurements and UV−vis titrations. The results obtained are summarized in Table 2. From the four expected protonation steps of the free ligand (L4−), only one corresponding to the protonation of one of the

Figure 1. UV−vis titration of a 10−5 M solution of L in the pH range 5.0−1.0.

With this data set, and using a nonlinear fitting software,26 an equilibrium constant with a value of 1.91(2) (pKa1) logarithmic units was determined, corresponding to the second protonation step of the carboxylate moieties. As the data available in the literature on the acidity of oxamic acids are scarce, a potentiometric titration of the oxamic acid was carried out for comparison purposes obtaining values of 1.92(1) and 11.8(1) for pKa1 and pKa2 (0.15 M NaCl and 25 °C). It should be noted that the values of pKa1 for H4L and oxamic acid are practically identical. The other two deprotonation constants of the H4L ligand could not be determined by potentiometric titration because, as has been described before, values of pH greater than 11.0 are required to deprotonate the oxamide group from N-substituted oxamides; this very weak acidity hinders their determination by this technique.40 However, in the presence of Cu(II), the deprotonation of the oxamides/oxamates to form the oxamidate/oxamate dianions takes place at a much lower pH range, allowing their potentiometric determination.41 On the D


Article

Inorganic Chemistry

(6.703 Å).43 Another hydrogen bond between the free water molecule of 1 and an amidate-oxygen atom [O2w···O4 = 2.809(12) Å] contributes to the stabilization of the structure. The two pyridyl rings of the 12-membered metallaaza-linked [3.3] metallacyclophane ring system are practically parallel, with a small angle between them of 8.49(14)°, besides exhibiting a staggered disposition with a separation between their centroids of 3.33(2) Å [interring carbon−carbon distances in the range 3.249(6)−3.600(8) Å]. The mean basal planes of the copper atoms of the dicopper(II) unit are orthogonal with the value of the dihedral angle they form being 88.44(15)°. However, they are far from being orthogonal with the planes of the pyridyl rings [dihedral angles of 63.41(14)° and 69.86(14)° between the plane calculated through N2, O3, Cu1ii, N3ii, O6ii, and those calculated through either N1, C1−C5 or N1ii, C1ii− C5ii, respectively]. This nonplanar conformation of the mpyba ligands in 1 is accommodated by a considerable twist of the C− N bonds between the pyridyl-carbon and the amide nitrogen atoms [torsion angles of 103.8(5)° for Cu1−N3−C5−N1 and −47.3(6)° for Cu1ii−N2−C1−N1]. The angles at the amidatenitrogen atoms [113.5(4)−125.2(3)° (at N2) and 112.0(4)− 128.5(3)° (at N3)] remain close to the value expected for trigonal rather than tetrahedral hybridization. Three (CH3)4N+ cations are present in the structure with two of them being disordered over two sets of 50% occupancy sites. One of these disordered cations has its nitrogen (N3C) on an inversion center, resulting in two interpenetrated tetrahedral molecules, whereas another one is present with its nitrogen N2C far away from an inversion center by 1.423 Å. In both cases, the occurrence of one molecule with 50% occupancy does exclude the centrosymmetry-related counterpart. The dicopper(II) metallacyclophane anions are wellisolated from each other in 1 due to intercalation between them by the integer tetramethylammonium cations with the shortest intermolecular Cu1−Cu1vi separation being 7.9599(10) Å (see Figure 3a). Channels of disordered (CH3)4N+ counterions in 1 are assembled along the crystallographic c axis as shown Figure 3b. (Me4N)4[K2Na2Cu4(mpyba)4(H2O)6.8]·1.6H2O (2). The dicopper(II) metallacyclophane present in 1 also occurs in 2 with the same five-coordination around each copper(II) ion and identical symmetry relations (a C2 local symmetry, the 2fold axis passing through the midpoint of the vector linking the two coordinated water molecules) (see Figure 4). The value of τ of the square pyramidal surrounding of the crystallographically independent copper(II) in 2 is 0.017, and those of the bond lengths in its basal plane are 1.963(3) (Cu1− N2i) and 1.971(4) Å (Cu1−N3)] and 1.964(3) (Cu1−O6) and 1.970(3) Å (Cu1−O3i). These bond distances are shorter the apical copper to water bond [Cu1−O3wi = 2.549(17) Å] with the water molecule of 20% occupancy. The basal plane of the square pyramid in this case is less distorted than in 1 [rms deviation of 0.103 Å for O3 with deviation of 0.114(4) Å for N2]. The two pyridyl rings of the 12-membered metallaazalinked [3.3] metallacyclphane ring system in 2 are practically parallel (angle of 8.95(14)°), and they exhibit a quasi-eclipsed disposition with a separation between their centroids of 3.43(2) Å [interring carbon−carbon distances in the range 3.318(6)− 3.660(8) Å]. The mean basal planes of the copper atoms of the dicopper(II) unit form a dihedral angle of 70.4(7)°, and they are quasi-orthogonal with the mean plane of the pyridyl ring [dihedral angles of 81.24(12) and 88.58(12)° between the plane calculated through N2i, O3i, Cu1, N3, O6, and those

basis of all the values obtained for the equilibrium constants in the present case (see Table 2), the distribution diagram for an equimolar mixture of H4L and Cu(II) shown in Figure S1 was obtained. One can see therein that the formation of the dicopper(II) complex [Cu2L2] occurs at pH values above 8.0, and it is the prevailing species above pH 9.0. A rough estimate of the equilibrium constant for the formation of this species through the eq 2L + 2Cu ⇆ Cu2L2 can be obtained (log β ∼35.6) by considering two times the value of pKa2 of the oxamic acid [pKa2 = 11.80(1)] as the approximate cost for the full deprotonation of H2L. The great magnitude of this stability constant reveals that this ligand exhibits a high selectivity for the copper(II) ion, a feature that was already observed in previous reports concerning the complex formation between copper(II) ions and N,N′-substituted oxamides in water.41 Structural Descriptions: Crystal Structure of (Me4N)4[Cu2(mpyba)2(H2O)2]·H2O (1). The structure of 1 consists of dicopper(II) metallamacrocycle entities of the [3.3] metallacyclophane type of formula [Cu2(mpyba)2(H2O)2]4− (Figure 2) plus tetramethylammonium counterions. Each

Figure 2. Perspective view of the dicopper(II) metallacyclophane unit [Cu2(mpyba)2(H2O)2]4− of 1 with the atom numbering of the copper(II) environment. Thermal ellipsoids are drawn at 50% probability level, and the hydrogen atoms are shown as capped sticks [symmetry code: (ii) = −x + 2, y, −z + 0.5].

copper(II) ion is five-coordinate in a square pyramidal CuN2O3 surrounding with the value of the trigonality parameter (τ) being 0.27 (τ = 0 and 1 for ideal squarepyramidal and trigonal-bipyramidal, respectively).42 Two amidate-nitrogen [Cu−N = 1.957(4) and 1.964(4) Å] and two carboxylate-oxygen atoms [Cu−O = 1.941(5) and 1.969(5) Å] from two oxamate fragments related by a 2-fold rotation axis build the basal plane, and a water molecule [Cu− Ow = 2.554(8) Å] occupies the apical position. The values of the copper to oxamate-nitrogen/oxygen in 1 agree with those previously reported for the parent copper(II) complexes of formula Na4[Cu2(mpba)2]·10H2O20b and Na10[{Cu2(mpba)2}2(μ1,1-N3)2]·18H2O.43 The basal plane in 1 is distorted [rms deviation of the five coplanar atoms is 0.411 Å with the greatest deviation of 0.519(6) Å for O3]. This is a consequence of the hydrogen bond between the coordinated water molecule and the pyridyl nitrogen of the ligand [O3w··· N1 = 2.854(7) Å], as shown in Figure 2. In fact, this dual role of each water molecule as a donor group in the copper coordination and hydrogen bonding formation with the pyridyl-nitrogen atom in 1 does become the structure of the [Cu2(mpyba)2]4− building block, which is significantly constrained. This constraint can be noted in the shorter intramolecular copper−copper distance in 1 [Cu1···Cu1ii = 6.2529(8) Å] compared to those in Na4[Cu2(mpba)2]·10H2O [6.822(2) Å]20b and Na10[{Cu2(mpba)2}2(μ1,1-N3)2]·18H2O E


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Inorganic Chemistry

Figure 3. (a) A view of the crystal packing of the dicopper(II) metallacyclophane units in the bc plane for 1 [symmetry code: (vi) = −x + 2, −y + 1, −z + 1]. (b) Overall crystal packing of 1 with the tetramethylammonium channels highlighted in blue. The hydrogen atoms are omitted in the two views for the sake of clarity, and the non-hydrogen atoms are shown as either arbitrary radius spheres in (a) or capped sticks in (b).

Å (Figure 4). The cages are locked at their sides by means of coordination to univalent potassium and sodium cations through the carboxylate oxygens from the oxamate groups (Figure S3). Both potassium and sodium atoms have 50% occupancy due to their localizations on the mirror plane parallel to (100). They are reflected on themselves to generate the full occupancy position. Each potassium atom (K1) is sevencoordinate with an out-of-the cage water molecule (which is also bound to the sodium atom) and six carboxylate oxygens, four of which (O3i, O3iv, O6, O6iii) are from two building blocks of the same cage that are coordinated to two copper atoms and the other two (O2i, O2iv) from a neighboring cage stacked parallel to the crystallographic b axis, being not coordinated to copper(II) but acting as donors toward the sodium atom (Na1). The crystallographically independent Na(1) atom is five-coordinate in a square-pyramidal geometry. Its basal plane is slightly distorted [rms deviation of the five coplanar atoms is 0.347 Å with the greatest deviation of 0.346(3) Å for Na1], and it is built by the two carboxylate oxygens aforementioned and two mirror plane symmetry related out-of-the cage water molecules (O1w). The apical position is occupied by the water molecule also coordinated to the potassium atom (Figure S3). The oxygen of this water molecule has 50% occupancy due to its positioning on the mirror plane parallel at (100), similarly to the potassium and sodium cations. The other two noninteger water molecules are hosted into the cage beside that coordinated to copper(II). They are on sites of either 50% [acting as hydrogen bonding donors toward two pyridyl-nitrogen atoms from two mpyba ligands forming a dicopper(II) metallacyclophane] or 15% occupancy [acting as hydrogen bonding donor toward the two carboxylate-oxygens O3 and O6, which are coordinated to the same copper(II) ion] (Figure S3). The oxygen of the water

Figure 4. A perspective view of the [Cu2(mpba)2]4− fragment in 2. Non-hydrogen atoms are shown as 50% probability ellipsoids, and they are arbitrarily numbered. Hydrogen atoms are shown as capped sticks [symmetry code: (i) = x, −y, −z + 1].

calculated through either N1, C1−C5 or N1i, C1i−C5i, respectively]. As observed in 1, this nonplanar conformation of the mpyba ligands in 2 is accommodated by a considerable twist of the C−N bonds between the pyridyl-carbon and the amide nitrogen atoms [torsion angles of 76.0(4)° for Cu1− N3−C5−N1 and −86.8(5)° for Cui−N2−C1−N1]. The angles at the amidate-nitrogen atoms [114.4(2)−130.2(3)° (at N2) and 114.3(3)−130.0(3)° (at N3)] remain close to the value expected for trigonal rather than tetrahedral hybridization. The coordinated water molecule O3wi is cached into the cage structure formed by two [Cu2(mpyba)2]4− building blocks, which are front-to-front assembled through a mirror plane (Figure S2). These two dicopper(II) metallacyclophane anions are very close to each other, as shown by the short separation between their copper atoms [Cu1···Cu1iii = 5.420(4) Å (Figure S3b)] in comparison with the Cu1···Cu1i distance of 6.507(8) F


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Inorganic Chemistry

Figure 5. (a) Side and (b) top views of three cross-locked cages giving rise to chains of 2 running parallel to the crystallographic b axis. The out-ofthe cage water molecules are also included in (a) and (b). Non-hydrogen atoms are shown as 30% probability ellipsoids and the hydrogen atoms are drawn with arbitrary radius spheres. (c) Overall crystal packing of 2 with the channels of the tetramethylammonium are highlighted in blue. The 1D coordination polymer grows as the projection shown onto the ac plane. Only intermolecular contacts between polymeric chains stacked along the crystallographic a axis occur in 2.

molecule hydrogen bonded to the pyridyl-nitrogens is on a 2fold rotation axis and therefore has a 25% occupancy. This whole water fraction consequently has 50% occupancy, and it is found twice on the cage structure. The other two water fractions are found in four equivalent symmetry positions in the cage, summing over 2.4 water molecules either hydrogen bonded or coordinated into the cage. In summary, the uncommon oligonuclear, mixed-valent heterometallic Cu(II)/K(I)/Na(I) cage structure therefore has the general formula [Na2K2Cu4(mpyba)4(H2O)8.4]4− with the charge balance being ensured by four out-of-the cage (CH3)4N+ cations per cage unit. Indeed, the overall asymmetric unit of 2 is a quarter of one cage unit as described and one (CH3)4N+ counterion distributed into two sets of occupancy sites on special positions. Two tetramethylammonium cations with 50% occupancy nitrogen atom are stacked along the crystallographic a and c axes forming true counterion channels, which contribute to the packing of the chains made up by joined cages (Figure 5c). These nitrogen atoms of the (CH3)4N+ cations are found either on the mirror plane parallel to the (100) plane (N1C) or on the 2-fold rotation axis parallel to the crystallographic b axis (N2C). In fact, a 1D coordination polymer is assembled with interlinked cage structures once the sides of neighboring cages are cross-locked with common potassium ions (Figure 5a and b). [Na6Cu2(mpyba)2Cl2(H2O)8]·7H2O (3). We have also performed the synthesis of a dicopper(II) metallacyclophane using sodium hydroxide instead of tetramethylammonium hydroxide. As a result of this procedure, another coordination polymer was obtained where the dicopper(II) metallacyclophane [Cu2(mpyba)2]4− building block occurs as in 1 and 2 (Figure 6). Half of this entity is in the asymmetric unit, whereas the other half symmetry is related by a mirror plane. The crystallographically independent copper(II) ion in 3 (Cu1) is five-coordinate in a square pyramidal surrounding as in 1 and 2. The basal plane formed with two nitrogen and two oxygen atoms from the two oxamate donor groups of two ligands is kept in 3 [rms deviation of the five coplanar atoms is 0.161 Å with the greatest deviation of 0.154(3) Å for N2], but a chloride anion occupies the apical position at the Cu1 in 3

Figure 6. Perspective view of the dicopper(II) metallacyclophane building block in 3. Non-hydrogen atoms are shown as 50% probability ellipsoids, and they are arbitrarily labeled. Hydrogen atoms are shown as capped sticks [symmetry code: (vii) = x, y, −z + 0.5].

instead of a water molecule in 1 and 2. Another difference between these building blocks is the fact that the apical position of coordination to copper is, relative to the coordination basal plane, on the opposite side of the pyridyl-nitrogen in 3, whereas it is on the same side in 1 and 2. This is related to the face-toface orientation of the building blocks into the polymeric sheets of 3 (see below). The two pyridyl rings of the 12-membered metallaaza-linked [3.3] metallacyclophane ring system in 3 are practically parallel [angle of 8.55(12)°], and they exhibit an eclipsed disposition with a separation between their centroids of 3.36(3) Å [interring carbon−carbon distances in the range 3.226(4)−3.573(4) Å]. The mean basal planes of the copper atoms of the dicopper(II) unit form a dihedral angle of 57.40(14)°, and they are quasi-orthogonal with the mean plane of the pyridyl ring [dihedral angles of 82.45(11) and 89.94(12) between the plane calculated through N2, O3, Cu1, N4, O6, and those calculated through either N1, C1−C3, C1vii, C2vii or N3, C6−C8, C6vii, C7vii, respectively]. As observed in 1 and 2, this nonplanar conformation of the mpyba ligands in 3 is accommodated by a considerable twist of the C−N bonds between the pyridyl-carbon and the amide nitrogen atoms [torsion angles of 90.8(4)° for Cu1−N2−C1−N1 and −96.3(3)° for Cu1−N4−C6−N3]. The angles at the G


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Inorganic Chemistry

Figure 7. (a) View of a fragment of the layer structure of 3. The Na6 and Na6vii atoms are in an exclusion zone of a mirror plane symmetry, owing 50% occupancy to each, and then they are mutually exclusive. (b) Perspective view illustrating the role of the Na3 atom in the stabilization of the layer. Water molecules and hydrogen atoms were omitted for clarity. All atoms are drawn with arbitrary radii spheres in (a) and (b) [symmetry code: (vii) = x, y, −z + 0.5; (viii) = x, −y + 1.5, −z; (ix) = x, −y + 0.5, −z; (x) = x, y, −z − 0.5].

coordinate with their surroundings being built by the O1, O1ix, O2, O2ix, O5xi, and O5xii oxamate oxygens (Na1) and the O4, O4viii, O5, and O5viii plus two water molecules (O1w and O1wviii), which are related by a 2-fold rotation axis (Na2) (Figure S4a and b). The connection between Na1 and Na2xii through O5xii and O5xi leads to a double layer motif in 3. In fact, the Na3, Na4, Na5, and Na6 atoms are arranged into coordination wires growing along the crystallographic b axis due to double coordination of O4w and O5w water oxygens to Na4 and Na5 atoms from two layers (Figure S5), which act to bridge them together with the Na1 coordination layout. In these wires, the coordination environment of Na4 and Na5 is also octahedral. Each of them is bonded to two carbonyl oxygens of the oxamate group from neighboring dicopper(II) metallacyclophanes (O5 and O5x to Na4 and O2 and O2x to Na5, see Figure 7a), meaning the bridging between the building blocks and to four water oxygens of 50% occupancy each. There are six water oxygens (O2w, O3w, O4w, O5w, O6w, andO7w) with this occupancy residing on the same mirror plane as the sodium atoms, all of which are coordinated to the sodium atoms. The Na6 atom has a five-coordinated environment, being bonded to two oxamate oxygen atoms of the same building block, which are also coordinated to the copper(II) ion and to three water oxygens placed on the mirror plane of the sodium atoms. The Na3 atom is bound to one water oxygen and to two chloride anions. It is striking to observe the short

amidate-nitrogen atoms [112.7(2)−131.0(2)° (at N2) and 114.58(2)−128.81(2)° (at N4)] remain close to the value expected for trigonal rather than tetrahedral hybridization as in 1 and 2. The dicopper(II) metallacyclophane unit in 3 acts as a ligand through the O1O2O4O5O1viiO2viiO4viiO5vii set of oxygen atoms toward sodium(I) cations to afford a neutral heterobimetallic Cu(II)−Na(I) 2D structure that grows in the bc plane (Figure 7a). In fact, six crystallographically independent sodium atoms are found in the asymmetric unit with 50% occupancy. Two of them (Na1 and Na2) are on the 2-fold axis running along the crystallographic a axis, whereas the other three (Na3, Na4, and Na5) are on the mirror plane parallel to (001) (Figure 7b). They are either rotated or reflected on themselves to generate the full occupancy position. Another 50% occupancy sodium atom (Na6) is separated by 0.8625 Å from the same mirror plane containing the Na3, Na4, and Na5 atoms. The occurrence in one site of the Na6 atom does exclude the mirror symmetry related position due to the short distance between them of 1.725 Å. The Na1 and Na2 sodium atoms are responsible for assembling the zigzag chains along the crystallographic b axis through binding to the O1O2O4O5 carbonyl-oxygen atoms of the mpyba ligand (Figure 7a). Each of these two sodium atoms are coordinated to four oxamate oxygens, acting as bridges between dicopper(II) metallacyclophanes. The Na1 and Na2 atoms are both sixH


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Inorganic Chemistry distance between the Na3 and Na6 atoms [∼2.442(7) Å; Figure 7b]. The shortest separation between the copper(II) atoms within the double layer is 4.3191(8) Å (Cu···Cuxii; Figure S4a), a value shorter than the Cu···Cuvii distance in the dicopper(II) metallacyclophanes [6.9072(7) Å, Figures 6 and Figure S5). This is a consequence of the fact that the building blocks of the connected layers are face-to-face oriented (Figure S4). In addition, there are four crystallographically independent crystallization water molecules packed between the coordination sheets along the crystallographic a axis (Figure S4b). One of them has its oxygen atom on a 2-fold rotation axis, and therefore its site occupancy is 50%. The interconnection of the double layers through the crystallization water molecules contributes to the stabilization of the three-dimensional supramolecular structure of 3. Magnetic Properties of 1−3. The magnetic behavior of 1−3 under the form of χMT versus T plots [χM is the magnetic susceptibility per two copper(II) ions] is shown in Figure 8 (1),

χM || = [2Nβg 2 /k(T − θ )][exp( −D/3kT ) /{exp(2D/3kT ) + 2exp( −D/3kT ) + exp( −J /kT )}] (2)

and χM ⊥ = (2Nβg⊥2 /D)[{exp(− 2D/3kT ) − exp(−D /3kT )} /{exp(2D/3kT ) + 2exp( −D/3kT ) + exp( −J /kT )}] (3)

which is derived through the spin Hamiltonian of eq 4 and takes into account the intermolecular magnetic interactions (θ) and the zero-field splitting of the S = 1 spin ground state (D). H = −JSCu1·SCu2 + SCu1·D·SCu2 + β(SCu1·gCu1 + SCu2·gCu2) ·H

where J is the magnetic coupling parameter, and gCu1 = gCu2 = g is the average Landé factor, which is assumed to be isotropic (g|| = g⊥= g). Because of the large correlation between the two parameters D and θ, it is not possible to obtain unambiguous values for both parameters. Thus, we performed the fitting process for the two limiting cases: D = 0 and θ = 0. Least-squares best-fit parameters are J = +6.85 cm−1, g = 2.10, and D = 2.50 (or θ = −0.38 K) for 1, J = +7.40 cm−1, g = 2.08, and D = 2.30 cm−1 (or θ = −0.29 K) for 2, and J = +7.90 cm−1, g = 2.09, and D = 2.40 cm−1 (or θ = −0.33 K) for 3. The theoretical curves follow the experimental data of 1−3 in the whole temperature range. The values obtained for D and θ are the upper limits for these parameters. However, because of the fact that the copper(II) ions from different dicopper(II) metallacyclophanes in 1−3 are well-separated from each other (see above), no relevant intermolecular magnetic interactions are expected. To substantiate the magnitude and sign of the intramolecular magnetic couplings (values of J) and visualize the exchange pathway involved, we carried out DFT-type calculations on models built from the experimental geometries of 1−3 (see Figure S8). The calculated values of J are +6.3 (1), +7.0 (2), and +7.7 cm−1 (3). The fact that they are very close to those extracted by fit of the experimental magnetic susceptibility data gives additional support to both the ferromagnetic nature and quasi-identical strength of the magnetic interaction in these dicopper(II) metallacyclophane entities of 1−3. Also, the remarkable ferromagnetic coupling observed between the two copper(II) ions separated by more than 6.2 Å through the mpyba ligand is a result of spin polarization effects through the π-pathway onto the bridging skeleton. This is confirmed by an alternating distribution of spin densities on the pyridine group of the ligand charge on the transmission of the magnetic coupling (see Figure 9), such as those expected in a metaderivative phenyl spacer and in agreement with previous magneto-structural studies on polynuclear metal complexes.20b,46−51 Because the spin polarization mechanism governs the intramolecular magnetic coupling between copper(II) ions, the injection of spin density from the copper(II) ion to the 2p orbitals of the metal-substituted pyridyl spacer is crucial. Thus, an angle between the Cu−Namidate vector and the mean plane of the pyridyl spacer (γ) close to 90° together with a high planarity of this spacer are the ideal conditions to transmit the ferromagnetic coupling. That is why the more 1 and less distorted 3 complexes [γ = 74.5 and 47.3° (1), 76.0 and 86.8°

Figure 8. Thermal dependence of the χMT product for 1: (o) experimental; (__) best-fit curve through eqs 1−3 (see text). The inset shows details of the low temperature region.

Figure S6 (2), and Figure S7 (3). At room temperature, χMT is equal to 0.83 (1), 0.80 (2), and 0.82 cm3 mol−1 K (3), values that are close to those expected for two magnetically isolated copper(II) ions. Upon cooling, χMT continuously increases to reach maximum values of 0.99 (1), 1.01 (2), and 1.03 cm3 mol−1 K (3) at 3.5 (1), 5.0 (2), and 5.0 K (3), and it further decreases to ∼0.93 (1 and 2) and 0.91 cm3 mol−1 K (3) at 1.9 K. The shape of these plots is characteristic of a ferromagnetic coupling within the dicopper(II) metallacyclophane unit of 1− 3; the maxima in χMT at low temperatures is due to zero-field splitting effects and/or weak intermolecular antiferromagnetic interactions. Another fact that can induce a maximum in χMT is the use of too large external applied magnetic fields.44 For avoiding these saturation effects by the applied magnetic fields, we have used very low fields (0.05 and 0.1 T, see Physical Measurements), and we determined that the magnetic susceptibility was not field dependent for magnetic fields lower than 0.75 T. With this in mind, the magnetic data of 1−3 were treated though the following expression [eqs 1−3]45 χM = (χM || + 2χM ⊥ )/3

(4)

(1)

with I


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Inorganic Chemistry

structures that can be obtained in the presence of poorly coordinating alkaline cations (compound 2 and 3), which act as linkers of the discrete dicopper(II) metallacyclophane unit occurring in 1, where they are isolated from each other by the organic tetramethylammonium cation. Finally, the study of the magnetic properties of 1−3 complemented by DFT-type calculations shows that relative important ferromagnetic couplings between copper(II) ions separated by more than 6.2 Å in metallamacrocycles of the [3,3] metallacyclophane type can be achieved through the spin polarization mechanism (compounds 1−3). Finally, the ability to mediate ferromagnetic interactions between two copper(II) ions through the -Namidate(C-C-C)phenyl-Namidate- exchange pathway in the context of the spin polarization mechanism, which is represented by the complex Na4[Cu2(mpba)2]·10H2O, is decreased when a nitrogen atom is included in the aromatic ring of the exchange pathway, that is, -Namidate-(C-N-C)pyridyl-Namidate-, as illustrated by compounds 1−3.

Figure 9. Spin density distribution in the dicopper(II) metallacyclophane fragment of 3. Blue and yellow colors represent positive and negative isodensity surfaces with a cutoff value of 0.0014 e bohr−3.

(2), and 88.7 and 82.7° (3)] exhibit the relative weaker and stronger magnetic couplings, respectively. Other structural parameters, such as the shift of the copper(II) ion from square basal [0.180(3) (1), 0.081(4) (2), and −0.125(3) Å (3)] and the tetrahedral distortion of this plane [23.86(19) (1), 6.81(13) (2), 10.10(11)° (3)], will also contribute to weaken the magnetic coupling, as these structural distortions being more accentuated in 1 would cause a somewhat weaker magnetic coupling in this compound with respect to 2 and 3. The question at hand was if the introduction of a nitrogen atom in the meta-substituted aromatic ring would strengthen or weaken the ferromagnetic coupling previously observed through the meta-substituted phenyl pathway in compound Na4[Cu2(mpba)2]·10H2O (J = +16.8 cm−1).20b A comparison between the spin density distribution at the organic bridging skeleton for 3 (Figure 10a) and Na4[Cu2(mpba)2]·10H2O

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information material is available free of charge on the ACS Publications Web site . The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.5b02786. The synthesis and characterization of Et2H2mpyba, distribution diagram for the Cu-L system, structural details of 1−3, thermal dependence of the magnetic susceptibility for 2 and 3, molecular models of 1−3 used in the DFT calculations, and selected bond lengths, angles, and hydrogen bonds of 1−3 (PDF) Crystallographic data for 1 (CCDC 1053438), 2 (CCDC 1053437), and 3 (CCDC 1053439) (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. *E-mail: [email protected].

Figure 10. Schematic representation of the spin density distribution on the bridging pathway for (a) 3 and (b) Na4[Cu2(mpba)2]·10H2O on the basis of DFT calculations. Empty and full contours correspond to positive and negative spin densities. Calculated average atomic spin densities are given in parentheses.

Notes

The authors declare no competing financial interest.

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(Figure 10b) shows that the absolute value of the atomic spin densities on the atoms of the -Namidate-(C-N-C)pyridyl-Namidatebridging pathway in 3 are smaller than those of the -Namidate-(CC-C)phenyl-Namidate- sodium salt, and therefore the spin polarization mechanism is also more effective in this last compound, Na4[Cu2(mpba)2]·10H2O. This is well-reflected by the different values of the intramolecular ferromagnetic interaction that they exhibit (J = +16.8 and +7.90 cm−1 for Na2[Cu2(mpba)2]· 10H2O and 3, respectively).

ACKNOWLEDGMENTS This research was supported by the Ministério da Educaçaõ do Brasil for MCT/CNPQ (Project Universal no. 484997/2012-2 and Project casadinho-procad no. 552252/2011-5), CAPESDGU Brazilian-Spanish (Project no. 295/13-HB2014-00024), the Ministerio Español de Economiá y Competitividad (Project CTQ2013-44844P), and Unidad de Excelencia Ramiro de Maeztu (Project MDM-2015-0538). T.S.F., R.S.V., and A.K.V. thank CAPES and CNPq for grants. Thanks are extended to ́ the Spanish Consejo Superior de Investigaciones Cientificas (CSIC) for the award of a license for the use of the Cambridge Structural Database (CSD). The authors are also grateful to Drs. Rafael Ruiz-Garciá and Emilio Pardo for stimulating discussions along this work. This study is dedicated to our friend and teacher Prof. Juan Faus for his outstanding contribution to progress in the coordination chemistry field as both a teacher and researcher.

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CONCLUSIONS The combined potentiometric and spectrophotometric study of complex formation between the N,N′-2,6-pyridinebis(oxamic acid) and the copper(II) ion in aqueous solution demonstrates the great selectivity of the mpyba ligand for this metal ion with the value of the inferred stability constant for the formation of the dicopper(II) species [Cu2(mpyba)2]4− being log β ∼35.6. Another important point arises from the diversity of the J


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Inorganic Chemistry

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