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Synthesis, Crystal Structures, and Magnetic Properties of Two Novel Cyanido-Bridged Heterotrimetallic {CuIIMnIICrIII} Complexes Maria-Gabriela Alexandru,*,† Diana Visinescu,‡ Sergiu Shova,& Marius Andruh,*,# Francesc Lloret,∥ and Miguel Julve*,∥ †

Department of Inorganic Chemistry, Physical Chemistry and Electrochemistry, Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, 1-7 Gh. Polizu Street, 01106 Bucharest, Romania ‡ Coordination and Supramolecular Chemistry Laboratory, “Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, Splaiul Independentei 202, Bucharest 060021, Romania & “Petru Poni” Institute of Macromolecular Chemistry, Romanian Academy, Aleea Grigore Ghica Vodă 41-A, RO-700487 Iasi, Romania # Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str. Dumbrava Rosie 23, 020464 Bucharest, Romania ∥ Departament de Química Inorgànica/Instituto de Ciencia Molecular, Universitat de València, C/Catedrático José Beltrán 2, 46980 Paterna, València, Spain S Supporting Information *

ABSTRACT: The self-assembly process between the heteroleptic [CrIII(phen)(CN)4]− and [CrIII(ampy)(CN)4]− metalloligands and the heterobimetallic {CuII(valpn)MnII}2+ tecton afforded two heterotrimetallic complexes of formula [{CuII(valpn)MnII(μ-NC)2CrIII(phen)(CN)2}2{(μNC)Cr III (phen)(CN) 3 } 2 ]·2CH 3 CN (1) and {[Cu II (valpn)Mn II (μNC)2CrIII(ampy)(CN)2]2·2CH3CN}n (2) [phen = 1,10-phenanthroline, ampy = 2-aminomethylpyridine, and H2valpn = 1,3-propanedyilbis(2iminomethylene-6-methoxyphenol)]. The crystal structure of 1 consists of neutral CuII2MnII2CrIII4 octanuclear units, where two [Cr(phen)(CN)4]− anions act as bis-monodentate ligands through cyanide groups toward two manganese(II) ions from two [CuII(valpn)MnII]2+ units to form a [{Cu(valpn)Mn}2Cr2(CN)4]6+ square motif. Two [Cr(phen)(CN)4]− pendant anions in 1 are bound to the copper(II) ions with cis−trans geometry with respect to the bridging [Cr(phen)(CN)4]− anion. Compound 2 is a sheet-like coordination polymer, where chains constituted by {CrIII(ampy)(CN)4} spacers act as bis-monodentate ligands toward the manganese(II) ions belonging to the {CuII(valpn)MnII} nodes, which are interlinked by another {CrIII(ampy)(CN)4} unit that acts as a bridge between the copper(II) and manganese(II) ions of adjacent chains. Magnetic susceptibility measurements in the temperature range of 1.9−300 K were performed for 1 and 2. An overall antiferromagnetic behavior is observed for 1, the ground spin state being described by a spin triplet from the square motif plus two magnetically isolated spin triplets from the two peripheral chromium(III) ions. Ferrimagnetic chains with interacting spins 1/2 (resulting spin of the trimetallic {CuII(valpn)MnII(μ-NC)CrIII} fragment) and 3/2 (spin from the bis-monodentate [CrIII(ampy)(CN)4]− with weak interchain ferromagnetic interactions across the cyanide bridge between the chromium(III) and the copper(II) ion from adjacent chains [θ = +3.83(2) cm−1]) occur in 2, resulting into a ferromagnetic ordering below 3.5 K. The values of the magnetic coupling between the Cu(II) and Mn(II) ions through the double phenoxide bridge [J = −63.1(2) (1) and −62(3) cm−1 (2)] and those between the Cr(III) and the Mn(II) across the single cyanide bridge [J = −7.08(5) and −4.86(6) cm−1 (1) and −8.59(3) cm−1 (2)] agree with the values reported for these exchange pathways in other magnetostructural studies.

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Cyanide-bearing complexes of the type [M(CN)x]y− [M = CrIII, FeIII, CoIII, RuIII, and OsIII (x = 6 and y = 3) and M = NbIV, MoIII/IV/V, WIV/V and Re IV/V, (x = 7, 8 and y = 4/ 3)],33−50 [MIIIL(CN)x]−,51−59 and [WIV/V(bpy)(CN)6]2−/− [L = bi- (x = 4) and tridentate ligands (x = 3)] were extensively

INTRODUCTION Coordination polymers (CPs) containing different spin carriers are of great interest in molecular magnetism.1−5 A plethora of heterobimetallic complexes have been described to date, while heterotrimetallic complexes are still rare.6−32 The self-assembly process involving a mononuclear metalloligand and a binuclear heterobimetallic complex represents an efficient method to construct heterotrimetallic coordination compounds.10−32 © XXXX American Chemical Society

Received: December 7, 2016

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DOI: 10.1021/acs.inorgchem.6b02966 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

Caution! Cyanides are highly toxic and dangerous. They should be handled in small quantities with great care. Synthesis of [{CuII(valpn)MnII(μ-NC)2CrIII(phen)(CN)2}2{(μ-NC)CrIII(phen)(CN)3}2]·2CH3CN (1). An acetonitrile solution (10 cm3) of PPh4[Co(phen)(CN)4]·H2O·MeOH (14 mg, 0.02 mmol) in acetonitrile (10 cm3) was poured slowly into another acetonitrile solution (10 cm3) containing [Cu(valpn)(H2O)2] (9 mg, 0.02 mmol) and Mn(NO3)2·4H2O (5 mg, 0.02 mmol). The resulting green solution was left undisturbed, and yellow-greenish platelike crystals were obtained after four days by slow evaporation in a hood at room temperature. Yield: ca. 55%. Anal. Calcd for C55H44Cr2CuMnN16O5 (1): C, 53.59; H, 3.57; N, 18.19. Found: C, 53.51; H, 3.52; N, 18.15%. IR (KBr/cm−1): 3438s [ν(H2O)], 2250w [ν(CNacetonitrile)], 2158w and 2137w [ν(CNcyanide)], and 1619vs, 1471s, 1305s, 459m, and 437m [ν(CN)]. Synthesis of {[CuII(valpn)MnII(μ-NC)2CrIII(ampy)(CN)2]2·2CH3CN}n (2). This compound was prepared by following the procedure used for 1, replacing PPh4[Co(phen)(CN)4]·H2O·MeOH by PPh4[Cr(ampy)(CN)4]·H2O (12 mg, 0.02 mmol). X-ray quality green cubelike crystals were obtained after three days on standing at room temperature in a hood. Yield: ca. 70%. Anal. Calcd for C43H42Cr2CuMnN16O4 (2): C, 48.25; H, 3.93; N, 20.94. Found: C, 48.45; H, 3.81; N, 20.88%. IR (KBr/cm−1): 3434s and 3239s [ν(NH2)ampy], 2250w [ν(CNacetonitrile)], 2155w and 2132w [ν(C Ncyanide)], and 1623vs, 1473s, 1250s, and 446m [ν(CN)]. Physical Measurements. Elemental analyses (C, H, N) were performed with a PerkinElmer 2400 analyzer. IR spectra were recorded with a FTIR Bruker Tensor V-37 spectrophotometer using KBr pellets in the range of 4000−400 cm−1. UV−vis diffuse reflectance spectra were recorded on a JASCO V-670 spectro-photometer. Direct current (dc) magnetic susceptibility measurements on crushed crystals of 1 and 2 (mixed with grease to avoid the crystallite orientation) were performed with a Quantum Design MPMSXL-5 SQUID magnetometer in the temperature range of 1.9−300 K and under applied dc magnetic fields of 5000 G (T ≥ 50 K) and 250 G (1.9 ≤ T ≤ 50 K). Magnetization versus H field measurements were done at 2.0 K in the field range of 0−5 T. Alternating current (ac) magnetic susceptibility measurements were recorded at low temperatures (2.0−8.0 K) under different dc static fields (0−5000 G) and ±5 G oscillating field at frequencies in the range of 5.0−1000 Hz. The magnetic susceptibility data were corrected for the diamagnetism of the constituent atoms and the sample holder (a plastic bag). The errors in the parameters from fitting the powder susceptibility data (see below) only reflect the degree of agreement between the experimental magnetic data and the calculated curve though the best-fit parameters, and they do not take into consideration the possible errors associated with the weighting, subtraction of the diamagnetic correction of the simple holder, and the sample itself or potential impurities. X-ray Data Collection and Structure Refinement. X-ray diffraction data for 1 were collected with an IPDS II STOE diffractometer equipped with graphite-monochromated Mo Kα radiation. Crystallographic measurements for 2 were performed with an Oxford Diffraction SuperNova diffractometer using high-flux microfocus Nova Cu Kα radiation. Data were processed with the CrysAlis PRO79 software. The structure was solved by direct methods using Olex280 software with the SHELXS structure solution program and refined by full-matrix least-squares on F2 with SHELXL-97.81 Atomic displacements for non-hydrogen atoms were refined using an anisotropic model. Hydrogen atoms were placed in fixed, idealized positions accounting for the hybridization of the supporting atoms and the possible presence of hydrogen bonds in the case of donor atoms. Additional details of the data collection and structural refinement parameters are provided in Table 1, whereas selected bond lengths and angles are listed in Table S1. Supplementary crystallographic information is available in the Supporting Information.

used as metalloligands.14,60−62 Among them, the heteroleptic cyanide-containing complex anions (which exhibit a lower symmetry and a smaller negative charge in comparison to their homoleptic analogues) allow the assembly of polynuclear complexes of different dimensionality and topology with respect to the systems generated by the homoleptic cyanido metalloligands. Chromium(III) tetracyanido complexes with bidentate blocking ligands such as phenanthroline (phen), 2,2′bipyridine (bpy), or aminomethylpyridine (ampy) were used as metalloligands to build heterobimetallic complexes: discrete molecules,63−67 ferrimagnetic {CrIIIMnII/III} chains,63,64,68−71 and {CrIIIMnII} CPs with mixed cyanide and dicyanamide/ oxalate/azide as bridges.72−74 However, to the best of our knowledge, there are no examples of heterotrimetallic complexes constructed from heteroleptic cyanide-bearing chromium(III) metalloligands. Most of the binuclear tectons used to assemble heterotrimetallic polynuclear complexes are 3d−4f systems, for example, {CuIILnIII}10−18,25,26,32 and {NiIILnIII}19,28−31,62 complexes with a side-off compartmental Schiff base ligand, synthesized from o-vanillin and various diamines. In most of the cases, the 3d and 4f metal ions interact ferromagnetically through the phenoxido bridge, and the uniaxial anisotropy of lanthanides, such as TbIII, DyIII, or HoIII, together with the resultant high-spin ground state make them good candidates for constructing molecular nanomagnets.10−13,15−19,28−32,62 Other heterobinuclear complexes that can be employed to construct heterotrimetallic complexes are the 3d−3d′ {CuIIMnII} building blocks with a dissymmetric macrocyclic Schiff-base ligand. Only two heterotrimetallic complexes based on 3d−3d′ tectons were reported to date, namely, chains with the general formula {CuIIMnIIL1(μ-NC)2MIII(bpb)}n [M = Fe or Cr; H2L1 is derived from the condensation reaction involving 2,6-diformyl4-methyl-phenol and ethylenediamine and diethylenetriamine; bpb = 1,2-bis(pyridine-2-carboxamido)benzenate].24 Nonetheless, the ability of the {CuIIMnII} moieties to act as nodes in several examples of heterobimetallic coordination polymers with organic molecules as spacers75−77 prompted us to explore their reaction with various cyanido metalloligands. In this paper we describe the synthesis, crystal structures, and magnetic properties of two new heterotrimetallic complexes: a m o l e c u l a r s q u a r e , n am e l y , [ { C u I I ( v a l p n ) M n I I ( μNC) 2 Cr III (phen)(CN) 2 } 2 {(μ-NC)Cr III (phen)(CN) 3 } 2 ]· 2CH3CN (1) and a two-dimensional network, namely, {[CuII(valpn)Mn II(μ-NC)2CrIII(ampy)(CN)2]2 ·2CH 3 CN} n (2) (H2valpn = the compartmental Schiff-base resulting from the 2:1 condensation of 3-methoxysalicyladehyde with 1,3propanediamine). The [Cr(phen)(CN)4]− metalloligand adopts mono- and bis-monodentate coordination modes in 1, whereas the parent [Cr(ampy)(CN)4]− building block acts as a bis-monodentate ligand in 2.

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EXPERIMENTAL SECTION

Materials. The chemicals used as well as the solvents were of reagent grade and were purchased from commercial sources. The starting compounds [Cu(valpn)(H2O)2], PPh4[Cr(ampy)(CN)4]· H2O, and PPh4[Cr(phen)(CN)4]·H2O·MeOH [H2valpn = 1,3propanediylbis(2-iminomethylene-6-methoxyphenol), and PPh4+ = tetraphenyphosphonium cation] were synthesized by following the literature procedures.68,78 The values of the Cr/Cu/Mn molar ratio (2:1:1) for 1 and 2 were determined by means of a Philips XL-30 scanning electron microscope (SEM) equipped with a system of X-ray microanalysis from the Central Service for the Support to the Experimental Research (SCSIE) at the University of València.

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RESULTS AND DISCUSSION Synthesis. The heterotrimetallic complexes 1 and 2 were prepared by the assembling reaction of the tetracyanido

B


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acetonitrile. The H2valpn behaves as a bicompartmental ligand and accommodates in the first compartment, {N2O2}, the CuII ion, leaving the second compartment, {O2O2}, available for the MnII ion. The binuclear unit, {CuIIMnII}, has been proven to be stable in reactions with various organic/inorganic ligands and metalloligands.76,77 The IR spectra of 1 and 2 show sharp medium bands in the 2000−2200 cm−1 region, which are assigned to the stretching vibrations of the terminal [2137 (1) and 2132 cm−1 (2)] and bridging cyanide groups [2158 (1) and 2155 cm−1 (2)]. The strong bands at 1619 cm−1 (1) and 1623 cm−1 (2) correspond to the imine bond stretching vibration [Supporting Information, Figures S1 (1) and S2 (2)]. The UV−vis spectra of 1 and 2 (Supporting Information, Figure S3) exhibit three bands in the visible region: (i) the first peak at ca. 450 nm with a shoulder at 370 nm (1 and 2), which correspond most likely to the electronic transitions 4A2g→4T2g and 4A2g→4T1g, respectively, of the chromium(III) ion82 and (ii) two other absorptions at 620 and 705 nm (1) and 590 and 685 nm (2) that could be tentatively assigned to the d−d transitions of the square pyramidal copper(II) ions.82 Description of the Crystal Structures. Compound 1 crystallizes in the triclinic space group P1̅. Its crystal structure consists of neutral CuII2MnII2CrIII4 octanuclear units, where two [Cr(phen)(CN)4]− anions [Cr1 and Cr1a; symmetry code: (a) = 1 − x, 1 − y, −z] act as bis-monodentate ligands toward the manganese(II) ions from two [CuII(valpn)MnII]2+ units forming a positively charged [CrIII2MnII2CuII2]2+ square. The charge balance is achieved by two monodentate [Cr(phen)(CN)4]− groups [Cr2 and Cr2a] that are bound to two copper(II) ions from the {CuII(valpn)MnII} corners (see Figure 1). The two crystallographically independent chromium(III) ions (Cr1 and Cr2) are six-coordinate with a bidentate phen molecule and four cyanide-carbon atoms building a distorted octahedral surrounding. The small bite angle of the chelating phen [79.93(12) and 79.79(12)° for N11−Cr1−N12 and N13−Cr2−N14, respectively] is the main factor accounting for this distortion from the ideal geometry. The values of the Cr− N(phen) [values in the range of 2.075(3)−2.087(3) Å] and Cr−C(cyanide) bond lengths [2.059(4)−2.100(4) (at Cr1) and 2.059(4)−2.074(4) Å (at Cr2)] agree with those reported

Table 1. Crystallographic Data, Details of Data Collection, and Structure Refinement Parameters compound empirical formula formula weight temperature/K crystal system space group a/Å b/Å c/Å α/deg β/deg γ/deg V/Å3 Z Dcalc/g cm−3 μ/mm−1 crystal size/mm3 θmin to θmax (deg) reflections collected independent reflections data/restraints/ parameters GOFc R1a [I > 2σ(I)] wR2b (all data) largest diff. peak/hole/ e Å−3

1 C55H44Cr2CuMnN16O5 1231.54 100.0(2) triclinic P1̅ 11.9138(6) 13.7775(6) 16.9147(7) 94.329(4) 101.311(4) 93.876(4) 2705.1(2) 2 1.512 6.058 0.08 × 0.07 × 0.02 6.456 to 133.198 19 173 9429 [Rint = 0.0446]

2 C43H42Cr2CuMnN16O4 1069.40 200.0(1) monoclinic P21/n 10.700(2) 17.661(2) 23.835(4) 90 100.378(13) 90 4802.4(14) 4 1.479 1.193 0.05 × 0.05 × 0.05 3.948 to 50.054 53 828 8442 [Rint = 0.1402]

9429/0/846

8442/5/564

1.025 0.0468 0.1243 0.77/−0.61

0.953 0.0462 0.0684 0.34/−0.76

R 1 = ∑∥F 0 | − |F c ∥/∑|F 0 |. b wR 2 = {∑[w(F 0 2 − F c 2 ) 2 ]/ ∑[w(F02)2]}1/2. cGOF = {∑[w(F02 − Fc2)2]/(n − p)}1/2, where n is the number of reflections, and p is the total number of refined parameters. a

metalloligand ([Cr(phen)(CN)4]− and [Cr(ampy)(CN)4]− for 1 and 2, respectively) and the preformed heterobimetallic {CuII(valpn)MnII} species in acetonitrile, resulting in a discrete octanuclear molecule (1) and a two-dimensional (2D) coordination polymer (2). The binuclear {CuII(valpn)MnII} species was generated in situ by reacting stoichiometric amounts of [CuII(valpn)(H2O)2] and Mn(NO3)2·4H2O in

Figure 1. (left) View of the asymmetric unit of 1, together with the atom numbering of the metal ions, and donor and cyanide-carbon atoms. (right) A view of the neutral heterotrimetallic square of 1. The solvent molecules of crystallization were omitted for clarity [symmetry code: (a) = 1 − x, 1 − y, −z]. C


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Inorganic Chemistry

Figure 2. π−π stacking interactions with the centroid−centroid distance of 3.31 Å. The Schiff-base ligand, three cyanide groups from each chromium(III) complex, and the acetonitrile solvent molecules were removed for clarity.

for the ionic salt PPh4[Cr(phen)(CN)4]·CH3OH·H2O63 and for the heterometallic complexes containing the [Cr(phen)(CN)4]− unit as a metalloligand.66−69 The values of the Cr− C−N angles for the bridging cyanides are 175.5(3) and 176.8(3)° for Cr1−C20−N3 and Cr1−C21−N4 and 173.7(3)° for Cr2−C24−N7, whereas those for the terminal ones vary in the ranges of 174.5(3)−179.2(4) (at Cr1) and 173.1(3)− 177.8(4)° (at Cr2). The peripheral [Cr2(phen)(CN)4]− group and its symmetry-related unit are connected to the copper(II) ions of the two [CuII(valpn)MnII]2+ entities from the corners of the {Cr2IIIMn2II} square through one cyanide ligand at the apical position. The values of the corresponding Cu1−N7 bond distance and Cu1−N7−C24 bond angle are 2.330(3) Å and 138.2(3)°, respectively. The chromium(III)−copper(II) separation across this bridge is 5.185 Å (Cr2···Cu1). The bismonodentate [Cr1(phen)(CN)4]− unit and its symmetryrelated entity are linked to the manganese(II) ions through two cyanide ligands filling one equatorial [Mn1−N3 = 2.205(3) Å] and an axial position [Mn1−N4a = 2.226(3) Å]. The values of the angles formed by these cyanide bridges at the manganese(II) ions are 177.1(3) (Mn1−N3−C20) and 168.2(3)° (Mn1−N4a−C21a) and those of the MnII···CrIII separation through them are 5.411 [Cr1···Mn1] and 5.429 Å [Cr1a···Mn1]. The copper(II) ion within the {CuII(valpn)MnII} binuclear fragment is located in the inner {N2O2} compartment of the Schiff-base ligand, while the manganese(II) ion occupies the outer {O2O′2} site. Each copper(II) ion in 1 is five-coordinate with two imine-nitrogen atoms (N1 and N2) and two phenoxide-oxygen atoms (O1 and O2) building the basal plane and one cyanide-nitrogen atom (N7) filling the apical position of a somewhat distorted square pyramidal environment. The value of the trigonality parameter (τ) is 0.05 (τ = 0 and 1 for ideal square pyramidal and trigonal biyramidal stereochemistry, respectively).83 Four oxygen atoms (O1, O2, O3, and O4) from the valpn2− ligand and one cyanide-nitrogen (N3) form the equatorial plane of the distorted pentagonal bipyramidal coordination geometry of each manganese(II) ion,

while the axial positions are occupied by one water molecule (O1W) and a cyanide-nitrogen atom (N4a). The values of the angles at the O1 and O2 phenoxido bridges are 106.86(10) (Cu1−O1−Mn1) and 105.82(10)° (Cu1−O2−Mn1), and the Cu1···Mn1 separation is 3.342 Å. The value of the dihedral angle at the double phenoxido hinge is 13.18°. These values lie within the range of those previously reported for other double diphenoxido-bridged CuII−MnII complexes.75−77,84−93 The crystal packing of 1 shows the presence of supramolecular chains of octanuclear units that grow along the crystallographic b axis through π−π-type stacking interactions (Figure 2). Moreover, hydrogen bonds between the coordinated water molecule (O1W) and two cyanide-nitrogen atoms (N7 and N8′) interlink the octanuclear units [2.938(4) and 2.838(4) Å for O1W···N7 and O1W···N8′, respectively; symmetry code: 1 − x, 1 − y, 1 − z] leading to supramolecular chains running parallel to the crystallographic c axis (Figure S4). The values of the shortest intermolecular metal−metal separations are 7.87 [Cr1···Cr1a], 7.90 [Cr1···Cr2′], and 7.12 Å [Mn1···Cr2′]. Compound 2 crystallizes in the monoclinic space group P21/n. Its structure consists of neutral layers of formula [CuII(valpn)MnII(μ-NC)2CrIII(ampy)(CN)2{(μNC)2CrIII(ampy)(CN)2}]n and acetonitrile molecules of crystallization. The asymmetric unit of 2 is made of two [CrIII(ampy)(CN)4]− metalloligands [Cr1 and Cr2] that are connected to the manganese(II) ion from the [CuII(valpn)MnII]2+ complex cation (Figure 3). One of these cyanidebearing chromium(III) spacers (Cr1) adopts a bis-monodentate coordination mode through two cis-positioned cyanide ligands connecting the Mn1 and Cu1a atoms [symmetry code: (a) = −3/2 − x, 1/2 + y, 1/2 − z] from adjacent chains along the crystallographic b axis to afford a neutral 2D motif that grows in the crystallographic ab plane. The other chromium(III) unit (Cr2) also act as bis-monodentate ligand but through two trans-positioned cyanide groups toward two manganese(II) ions [Mn1 and Mn1b; symmetry code: (b) = 1 + x, y, z] belonging to two neighboring heterobinuclear nodes leading to D


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Inorganic Chemistry

The {CuII(valpn)MnII} moiety in 2 results from the coordination of the compartmental Schiff-base ligand by the copper(II) ion located into the inner {N2O2} site and by the manganese(II) ion hosted in the outer {O2O2′} compartment. Each copper(II) ion in 2 is five-coordinate with two phenoxidooxygen (O1 and O2) and two imine-nitrogen atoms (N1 and N2) from the valpn2− ligand building the equatorial plane and a cyanide-nitrogen atom (N6a) in the apical site of a distorted square pyramidal environment. The value of the τ parameter for Cu1 is 0.011. The apical Cu1−N6a bond distance [2.7787(32) Å] is longer than the equatorial Cu1−N1 and Cu1−N2 bond lengths [1.967(4) and 1.969(4) Å, respectively]. The copper(II) ion is almost coplanar with the mean basal plane (the shift of the copper atom from the O1N1N2O2 mean plane is −0.1115 Å). The value of the angle at the copper atom of the cyanide bridge is Cu1−N6a−C23a = 135.2°, and the copper(II)−chromium(III) distance across this bridge is 5.565 Å (Cu1···Cr1a). Each manganese(II) ion is seven-coordinate in a distorted pentagonal bipyramidal geometry. The equatorial plane comprises two phenoxido (O1 and O2) and two methoxo (O3 and O4) oxygen atoms from the Schiff-base ligand and one cyanide-nitrogen atom (N3), whereas the axial positions are occupied by two other cyanide nitrogen atoms (N7 and N10b). The value of the Mn1−N10b, Mn1−N7, and Mn1−N3 bond lengths are 2.201(3), 2.191(3), and 2.245(4) Å, respectively. The angles subtended at the manganese(II) ion by the cyanide bridges are 159.7(4) (Mn1−N10b−C27b), 168.0(4) (Mn1−N7−C24), and 170.3(3)° (Mn2−N3−C20), and the values of the corresponding manganese(II)··· chromium(III) distances across them are 5.370 (Mn1···Cr1b), 5.352 (Mn1···Cr1), and 5.434 Å (Mn1···Cr2). The diphenoxido-bridged {CuII(valpn)MnII} unit in 2 has a roof shape as in 1, the value of the dihedral angle at the O1/O2 hinge in 2 being 3.72°. The copper−manganese separation within this unit is 3.326 Å, and the values of the angles at the phenoxido-oxygen atoms are 105.87(13) (O1) and 107.29(14)° (O2). Weak hydrogen bonds involving the amine group of the ampy molecule (N12) and the nitrogen atoms N8 and N4 from

Figure 3. View of the asymmetric unit of 2 showing the atom numbering of the metal ions, and donor and cyanide-carbon atoms [symmetry code: (a) = −3/2 − x, 1/2 + y, 1/2 − z; (b) = 1 + x, y, z].

a chain along the crystallographic a axis. In this way, each heterobimetallic {CuIIMnII} node is connected to four adjacent nodes by four tetracyanidochromate(III) metalloligands (Figure 4). The two crystallographically independent chromium(III) ions (Cr1 and Cr2) are six-coordinate by two nitrogen atoms from the bidentate ampy ligands [N11 and N12 (Cr1) and N13 and N14 (Cr2)] and by four cyanide-carbon atoms [C21−C23 (Cr1) and C24−C27 (Cr2)] building a distorted octahedral geometry. The values of the bite angle for the chelating ampy ligand are 80.47(13) (N11−Cr1−N12) and 81.17(17)° (N13− Cr2−N14). The Cr−C(cyanide) and Cr−N(ampy) bond distances vary in the ranges of 2.053(5)−2.087(5) (at Cr1)/ 2.030(6)−2.086(4) Å (at Cr2) and 2.062(11)−2.071(3) (at Cr1)/2.057(4)−2.077(4) Å (at Cr2). These values agree well with the reported ones for the ionic salt PPh4[Cr(ampy)(CN)4]·H2O and the 4,2-ribbonlike heterobimetallic chain {[Cr(ampy)(CN)4]2Mn(H2O)2·6H2O}n.68

Figure 4. View of a fragment of a layer of 2 growing the crystallographic ab plane. The valpn2− and ampy ligands, as well as two cyanido groups from each chromium(III) moieties, were omitted for clarity [symmetry code: (a) = −3/2 − x, 1/2 + y, 1/2 − z; (b) = 1 + x, y, z]. E


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Inorganic Chemistry terminal cyanide ligands [3.076(5) and 3.072(5) Å for N12··· N8 and N12···N4c, respectively; symmetry code: (c) = −2 − x, 1 − y, −z] interlink the neutral layers of 2 along the crystallographic a axis leading to a supramolecular threedimensional (3D) network (Figures 5 and S5). The closest interlayer distance between the chromium(III) ions is 6.78 Å [Cr1···Cr1c].

Figure 6. Temperature-dependent magnetic susceptibility data for 1: (○) experimental; (__) best-fit curve through eq 1 (see text). (inset) The low-temperature region in detail (the dotted and solid lines are the best-fit curves with θ = 0 and θ = −0.82 K, respectively.

Scheme 1. Intramolecular Exchange Pathways in 1

Figure 5. View of a fragment of the crystal packing of 2 showing the 3D supramolecular network through hydrogen bonds (red dots).

Although the asymmetric units of the two structures are similar [they contain the same building blocks, one heterobinuclear {CuII(valpn)MnII} fragment and two [CrIII(AA)(CN4]− metalloligands, with AA = phen (1) and ampy (2)], the coordinative bonds differ. In the case of 1, the manganese(II) ion is connected to two chromium(III) cyanidometallates, both in axial and equatorial positions, whereas the copper(II) ion is apically coordinated by the peripheral CrIII metalloligand. However, in the case of 2, two {CrIII(ampy)(CN)4} metalloligands connect axially to the manganese(II) ion, while a third chromium(III) unit coordinates to the same manganese atom in an equatorial position. In addition, a semi-coordinate bond is established through a cyanide bridge between the chromium(III) and the copper(II) ions. The geometric features of the metal ions and the structural parameters (bond distances and angles at the cyanido and double phenoxido bridges) in 1 and 2 are determinant factors of the magnetic behavior (see below). Magnetic Properties. The magnetic properties of 1 under the form of χMT versus T plot [χM is the magnetic susceptibility per octanuclear CuII2MnII2CrIII4 unit] are shown in Figure 6. At room temperature, χMT is equal to 15.0 cm3 mol−1 K, a value that is somewhat below the expected one for a set of two copper(II), two manganese(II), and four chromium(III) ions magnetically non-interacting (χMT = 2 × 0.375 + 2 × 4.375 + 4 × 1.875 = 17 cm3 mol−1 K with gCu = gMn = gCr = 2.0). When cooled, χMT continuously decreases to attain a value of 3.35 cm3 mol−1 K at 1.9 K. This trend is indicative of an overall antiferromagnetic behavior in 1. In the light of the octanuclear structure of 1, four intramolecular exchange pathways are involved as shown by Scheme 1: (i) the double phenoxido bridge between Cu1 and Mn1 (J1) and the single cyanide bridge between (ii) Mn1 and Cr1 (J2), (iii) Mn1 and Cr2 (J3), and (iv) Cu1 and Cr3 (j). Having this in mind, the magnetic data of 1 were analyzed through the isotropic spin Hamiltonian of eq 1

Ĥ = Ĥ exchange + Ĥ Zeeman ̂ SMn1 ̂ − J (SMn1 ̂ SCr1 ̂ + SMn2 ̂ SCr2 ̂ ) Ĥ exchange = −J1SCu1 2 ̂ SCr2 ̂ + SMn2 ̂ SCr1 ̂ ) − j(SCu1 ̂ SCr3 ̂ + SCu2 ̂ SCr4 ̂ ) − J (SMn1 3

̂ + SCu2 ̂ ) + g (SMn1 ̂ + SMn2 ̂ ) Ĥ Zeeman = βH[gCu(SCu1 Mn ̂ ̂ ̂ ̂ + g (SCr1 + SCr1 + SCr3 + SCr4)] Cr

(1)

where the first term accounts for the exchange coupling [J1, J2, J3, and j being the exchange coupling parameters of the exchange pathways (i), (ii), (iii), and (iv), respectively], and the second one corresponds to the Zeeman effects. The magnetic data of 1 were simulated by matrix diagonalization techniques using a Fortran program.94 In a first attempt, we kept constant j = 0 cm−1 and gMn = gCu = 2.0. A good match of the magnetic data was achieved in the temperature range of 300−22.0 K (dashed line in Figure 6) with the following best-fit parameters: [J1 = −63.1(2) cm−1], J2 = −4.86(6) cm−1, and J3 = −7.08(5) cm−1. In a second attempt, a successful reproduction of the magnetic data in the whole temperature range investigated was achieved (solid line in Figure 6) by keeping j = 0 cm−1 and gMn = 2.0 but introducing a Curie−Weiss term (θ), which takes into account the intermolecular magnetic interactions as well as the very small (if any) intramolecular copper(II)−chromium(III) interaction through the single cyanide bridge (j). The leastsquares best-fit parameters are θ = −0.82(1) K and gCu = F


Article

Inorganic Chemistry 2.10(1) with the values of J1, J2, and J3 being identical to those of the first fit. Given that a very weak spin density of the Cu1 atom is expected at the N7 atom, which fills the apical position [the unpaired electron of the copper(II) ion being delocalized in the basal plane defined by the N1N2O1O2 set of atoms], a very weak (if any) magnetic interaction between the chromium(III) and copper(II) through the (iv) pathway can be predicted. Consequently, the ground-spin state of 1 can be described by a spin triplet (S = 1) and two magnetically isolated spin quartets (S = 3/2) from each peripheral chromium(III) ion. In this sense, a plateau in the χMT curve with a value of 4.75 cm3 mol−1 K would be expected. This fact is shown in the inset of Figure 6 (dashed line with θ = 0). The decrease of the values of χMT below this plateau must be attributed most likely to intermolecular antiferromagnetic interactions (θ = −0.82 K). This description agrees with the magnetization curve, where a saturation value close tending to 8.0 μB is observed at 5 T (the maximum available magnetic field in our magnetometer; Figure 7). Such a value of the magnetization is the expected one for the contribution of a spin triplet (S = 1) plus two spin quartets (S = 3/2).

the two magnetic interactions between the chromium(III) and manganese(II) through the single cyanide bridges are concerned, the magneto-structural correlation established between the value of the Mn−N−C(cyanide) angle (α) and magnetic coupling (J in cm−1)) [JCrMn = −40 + 0.2α]64 leads to calculated values of −4.6 cm−1 for the Mn1−N3−C20−Cr1 pathway [α = 177.1(3)°] and −6.4 cm−1 for Mn1−N4a− C21a−Cr1a [α = 168.2(3)°]. Consequently, the values of J2 = −4.86(6) cm−1 and J3 = −7.08(5) cm−1 are unambiguously attributed to the Mn1−N3−C20−Cr1 and Mn1−N4a−C21a− Cr1a exchange pathways, respectively. The magnetic properties of 2 under the form of χMT against T plot [χM is the magnetic susceptibility per CuIIMnIICrIII2 unit] are shown in Figure 8. At room temperature, χMT is equal

Figure 8. χMT vs T plot for compound 2: (o) experimental; (__) bestfit curve through eqs 2 and (4) (see text). (inset) A detail of the lowtemperature domain.

to 8.30 cm3 mol−1 K, a value that is close to that expected for a set of one copper(II), one manganese(II), and two chromium(III) ions magnetically non-interacting (χMT = 0.375 + 4.375 + 2 × 1.875 = 8.50 cm3 mol−1 K with gCu = gMn = gCr = 2.0). When cooled, the values of χMT continuously decrease to reach a minimum value of 2.15 cm3 mol−1 K at ca. 16.0 K, and they further increase sharply. Finally, the magnetization achieves saturation (see Figure 9), and the values of χMT decrease linearly as shown in the inset of Figure 8. This behavior is characteristic of ferrimagnetic chains. Having in mind the structure of 2, the possible exchange pathways in this compound are the following: (i) the double

Figure 7. Magnetization vs H plot for 1 at 2.0 K. The solid line is only a guide.

A comment about the nature and magnitude of the magnetic interactions within the square motif of 1 is in order. The strongest magnetic coupling (J1 = −63.1(2) cm−1) is unambiguously attributed to the exchange interaction between the copper(II) and manganese(II) ions through the double phenoxido bridge. This value remains within the range of those reported for this pathway in analogous systems (−J = 14.0− 71.6 cm−1).75−77,84−93 The good overlap between the d(x2 − y2) magnetic orbital describing the unpaired electron of the copper(II) ion (the x and y axes being roughly defined by the copper to phenoxido-oxygen bonds) and the corresponding magnetic orbital at the manganese(II) ion mainly accounts for this relatively strong antiferromagnetic coupling. The values of the angle at the phenoxido-oxygen (γ) and the planarity of the diphenoxido-bridged copper(II)−manganese(II) core (measured by the value of dihedral angle ϕ at the O···O hinge) are the main factors determining the magnitude of this interaction. The influence of these parameters on the exchange coupling can be illustrated by comparing 1 [J = −63.1(2) cm−1 with values of γ and ϕ of 106 and 13.28°, respectively) with the compound {[Cu(H2O)(valpn)Mn(μ-ox)]·3H2O}n (ox = oxalate; J = −71.6 cm−1 with γ = 106° and ϕ = 4.11°).76 As far as

Figure 9. Magnetization vs H curves for 2 in the temperature range of 2.0−10.0 K. The solid lines are guides. G


Article

Inorganic Chemistry phenoxido-bridged copper(II)−manganese(II) unit (J1), (ii) two single cyanido-bridged Cr(III)−Mn(II) entities (J2 and J3), and (iii) a single cyanide-bridged chromium(III)−copper(II) pair (j) (see Scheme 2a). Because (i) and (ii) are known to Scheme 2. (a) Exchange Pathways in 2. (b) Ferrimagnetic Chain with Regular Alternating 3/2 and 1/2 Local Spins

Figure 11. Thermal dependence of the in-phase and out-of-phase ac susceptibility signals for 2 in the lack of applied external field and under an oscillating magnetic field of ±5.0 G at different frequencies. The solid and dotted lines are guides.

Heisenberg ferrimagnetic chains. For such chains, the value of β is shown to be close to 1. Further, the high-temperature behavior is well-described by an Arrhenius-like law giving the value of the Curie constant (C) when T→∞. ⎛ |J | ⎞ β ⎛ |J | ⎞ χM T = a⎜ ⎟ + C exp⎜ −b ⎟ ⎝ kT ⎠ ⎝ kT ⎠

mediate antiferromagnetic interactions, a spin doublet can be assigned to the Cu−Mn−Cr2 entity. In this sense, and neglecting the chromium(III)−copper(II) coupling (j = 0) due to the long apical Cu1···N6a(cyanide) interaction, a ferrimagnetic chain with alternating 3/2 and 1/2 local spins can be envisaged at low temperatures (Scheme 2b). The magnetization curve shows a saturation value of ca. 2.0 μB (Figure 9), a feature that supports this assumption. The field-cooled magnetization (FCM) shown in Figure 10 suggests a

|J | =

(2)

kTmin 1.19

(3)

For a ferrimagnetic chain Sa = 1/2 and Sb = 3/2 with ga = gb = 2.0, a value of β equal to 1.80 was determined and the value of J is related with the temperature at the minimum of the χMT curve through eq 3. Given that the χMT curve of 2 exhibits a minimum at 16.0 K, a value of J ≈ 9.0 cm−1 can be expected. To fit and discuss the magnetic properties of 2 through eq 2, two important considerations must be made: (a) in our case, the contribution of the second term of eq 2 will be replaced by the values of χMT obtained through the spin Hamiltonian of eq 4 ̂ SCu ̂ − J SMn ̂ SCr1 ̂ − J SMn ̂ SCr2 ̂ Ĥ = −J1SMn 2 3 ̂ + g SCu ̂ + g (SCr1 ̂ + SCr2 ̂ )] + βH[gMnSMn Cu Cr

(4)

which describes the magnetic properties of the tetranuclear {CuMnCr1Cr2} fragment (circle with dashed lines in Scheme 2a); (b) to avoid overparameterization, we will consider J2 = J3 (the same bridging ligand) and gMn = 2.0. Therefore, the J parameter in the first term of eq 2 will be J2. The least-squares best-fit parameters were gCu = 2.08(1), J1 = −62.3(1) cm−1, J2 = −8.53(3) cm−1, a = 0.34(1) cm3 mol−1 K, and β = 3.20(2). The value of J1 is very close to that found for the same double phenoxido-bridged {CuIIMnII} unit in 1. As far as the value of J2 is concerned, its value is similar to those calculated through the expression JCrMn = −40 + 0.2α)64 {values of −8.0 cm−1 for the Mn1−N10b−C27b−Cr2b pathway [α = 159.7(4)°], −6.3 cm−1 for Mn1−N7−C24−Cr2 [α = 168.0(4)°] and −5.9 cm−1 for Mn1−N3−C20−Cr1 [α = 170.3(3)°)]}. However, the value of the exponent β = 3.20 is clearly greater than that expected for a 1/2−3/2 alternating spin ferrimagnetic chain (β = 1.8, see above) suggesting that the magnetic dimensionality is higher than one-dimensional. In fact, these chains are interlinked through a single cyanide bridge connecting a

Figure 10. FCM for 2 under an applied dc field of 250 G. The solid line is only a guide.

ferromagnetic ordering below 3.5 K. This magnetic ordering is confirmed by the practically frequency-independent maxima in the in-phase and out-of-phase components of the ac magnetic susceptibility measurements around 3.5 K (Figure 11). Analytical expressions have been proposed to fit the theoretical variations of the magnetic susceptibility for the ferrimagnetic Heisenberg chains 1/2-S (S = 1, 3/2, 2, 5/2, and ∞) by considering two contributions [eq 2].95 First, the lowtemperature divergence of the χMT product can be described by a power law variation aTβ, in agreement with the findings of the H


Article

Inorganic Chemistry manganese(II) ion from one chain to a copper(II) ion from the adjacent chain (see Scheme 2a). The interchain magnetic coupling across the corresponding exchange pathway (Cr1a− C23a−N6a−Cu1, j) is expected to be small (due to the long axial Cu−N6a interaction) but ferromagnetic in nature (j > 0), and it would be responsible for the magnetic ordering observed for 2 below 3.5 K. In a second fit, the value of β was fixed to 1.80, and a Curie− Weiss parameter θ was introduced (in the form of T − θ) to take into account the interchain magnetic interactions. This fit gave θ = +3.83(2) K, the values of the other parameters being identical to those obtained in the previous fit. A value of j = +1.3 cm−1 can be calculated from that of the θ parameter by using the molecular field approximation. Both fits reproduce very well the experimental data (solid line in Figure 7), so we cannot determine the exact values of J2 and J3, since they are very correlated. Finally, it deserves to be noted that our approach allowed us to describe the magnetic behavior of compound 2 as ferrimagnetic chains with interchain ferromagnetic interactions.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. (M.-G.A.) *E-mail: [email protected]. (M.A.) *E-mail: [email protected]. (M.J.) ORCID

Marius Andruh: 0000-0001-8224-4866 Notes

The authors declare no competing financial interest. CCDC 1520091 (1) and 1520092 (2) are the supplementary crystallographic data for this article. They can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif.

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CONCLUSIONS Two {CuIIMnIICrIII} heterotrimetallic coordination compounds, 1 and 2, of different dimensionalities were synthesized by reacting the preformed hetero-dinuclear [CuII(valpn)MnII]2+ complex with the cyanide-bearing [Cr(phen)CN4]− and [Cr(ampy)(CN)4]− metalloligands, respectively. The structure of 1 consists of discrete [CuII2MnII2CrIII2]2+ hexametallic square cations with anionic [CrIII(phen)(CN)4]− pendant arms. Two {CrIII(phen)(CN)4} linkers act as bis-monodentate ligands toward the manganese(II) ions from the two {CuIIMnII} units within the square, while the other two chromium(III) metalloligands interact with the copper(II) ions belonging to the [CuII(valpn)MnII]2+ units through a single cyanide bridge. Compound 2 is a 2D neutral heterotrimetallic coordination polymer. Each {CuII(valpn)MnII} bimetallic node is connected to four adjacent nodes, by four {Cr(ampy)(CN)4} spacers, two of them acting as bridging ligands toward two manganese(II) ions belonging to two neighboring {CuII(valpn)MnII} binuclear nodes, and the other two, to the copper(II) and manganese(II) ions from two different {CuII(valpn)MnII} nodes. Antiferromagnetic interactions between the copper(II) and manganese(II) ions through the phenoxido bridge [J1 = −63.1(2) cm −1 ] and between the chromium(III) and manganese(II) ions through the cyanide bridge [J2 = −4.86(6) cm−1 and J3 = −7.08(5) cm−1] are exhibited in the case of 1. The magnetic coupling between the chromium(III) and manganese(II) ions could be correlated with the values of the Mn−C−N angles. The magnetic measurements indicate a ferrimagnetic behavior for compound 2 with a dominant strong antiferromagnetic interaction between the copper(II) and manganese(II) ions through the phenoxido bridge [J = −62(3) cm−1]. Moreover, because of the interchain magnetic coupling through the cyanide bridge connecting the copper(II) and chromium(III) metal ions, which are of ferromagnetic nature, magnetic ordering below 3.5 K occurs in 2.

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Refinement data (TXT) Refinement data (TXT) Tables of bond lengths and angles, IR, UV−vis spectra, and additional crystallographic drawings for 1 and 2 (PDF)

ACKNOWLEDGMENTS Financial support from the Romanian National Authority for Scientific Research, CNCS-UEFISCDI (Project Nos. PN-IIRU-TE-2014-4-1556 and PN-II-ID-PCCE-2011-2-0050), the Spanish MICINN (Project Nos. CTQ2013-44844-P and Unidad de Excelencia Mariá de Maetzu MD2015-0538), and the Generalitat Valenciana (PROMETEOII/2014/070) is gratefully acknowledged.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b02966. I


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