Polyhedron 171 (2019) 330–337

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Polyhedron
journal homepage: www.elsevier.com/locate/poly

Synthesis and characterisation of new Ni2Mn, Ni2Mn2 and Mn8 clusters

by the use of 2-pyridyl oximes
Constantinos G. Efthymiou a,b, Ioannis Mylonas-Margaritis b, Sayak Das Gupta c, Anastasios Tasiopoulos d,
Vassilios Nastopoulos e, George Christou c, Spyros P. Perlepes e, Constantina Papatriantafyllopoulou a,b,⇑
a
SSPC, Synthesis and Solid State Pharmaceutical Centre, Ireland
b
School of Chemistry, National University of Ireland Galway, H91 TK 33 Galway, Ireland
c
Department of Chemistry, University of Florida, Gainesville, FL 32611, United States
d
Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus
e
Department of Chemistry, University of Patras, Patras 26504, Greece

a r t i c l e i n f o a b s t r a c t

Article history: The initial employment of methyl 2-pyridyl ketoxime, (py)C(Me)NOH, in mixed metal Ni/Mn cluster
Received 5 May 2019 chemistry, provided access to complexes [NiII2MnIII{(py)C(Me)NO}6](ClO4) (1) and [NiII2MnIII 2 {(py)C(Me)
Accepted 18 July 2019 NO}6(OMe)2(MeOH)2](ClO4)2 (2) that display a linear and a zig-zag metal arrangement, respectively. 1
Available online 26 July 2019
and 2 are synthesized by reacting Ni(ClO4)26H2O, (py)C(Me)NOH, Mn(ClO4)26H2O and NaOMe in different
molar ratios (2:6:1:6, 1; 1:3:1:3, 2) in MeOH, and they are the first examples of 3d–3d0 mixed-metal clusters
Keywords: bearing (py)C(Me)NOH. The employment of phenyl 2-pyridyl ketoxime, (py)C(ph)NOH, instead of (py)C(Me)
2-Pyridyl oximes
NOH, provided access to the octanuclear homometallic compound [MnII4MnIII 4 O4(NO3)2{(py)C(ph)
3d–3d0 mixed metal clusters
NO}8(HCO2)2(MeOH)2] (3) that possesses a double-butterfly {MnII4MnIII 4 (l4-O)2(l3-O)2}
12+
Magnetism
core. 3 joins the
Ni/Mn compounds small family of Mn/(py)C(ph)NO clusters. Variable-temperature, solid-state dc and ac magnetic susceptibil-
Crystal structures ity studies were carried out on 1 and 2 and revealed the presence of antiferromagnetic exchange
interactions between the metal ions (JMn–Ni = 6.34 ± 0.14 cm1 in 1; JMn–Ni = 4.57 ± 0.08 cm1,
JMn–Mn = 12.72 ± 0.12 in 2) and a diamagnetic ground state for both compounds.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction Metal clusters have become the focus of intense investigation

over the last 30 years or so as they combine fascinating physical
Metal clusters or polynuclear metal complexes are hybrid properties and intriguing geometrical features, being related to a
metal–organic species, in which multimetallic entities are held variety of research fields including bioinorganic chemistry and
together through suitable organic ligands [1–3]. Their morpholog- molecular magnetism [5–14]. In the latter, the discovery that the
ical features follow a general structural/architectural pattern, con- compound [Mn12O12(O2CMe)16(H2O)4] (Mn12ac) could behave as
sisting of two distinct parts: (i) the inner metal core, MxYy (x = the a magnet at very low temperature, i.e. exhibiting single molecule
number of metal ions M, y = the number of donor atoms of the magnetism (SMM) behaviour, stimulated a new era in the field of
ligands or anions, Y, that bridge the metal ions), the structural molecular nanomaterials [5–7]. This compound contains a mixed
topology of which resembles with that of the minerals (oxides, valence manganese oxide unit (MnIII IV
8 Mn4 O12), which is coordinated
chlorides, sulfides. . .), and (ii) the outer organic cell consisting of peripherally to twelve acetate ligands. The oxide fragment bears the
the aliphatic and/or aromatic parts of the ligands. The latter encap- properties, such as magnetism, of the bulk infinite oxides, and com-
sulates the polar metal core, creating a hydrophobic protective bine them with exotic properties at the nanoscale level, as quantum
environment. Thus, the metal clusters can be described alterna- tunnelling of magnetization (QTM) and quantum phase interference,
tively as distinct fragments of infinite inorganic solids (minerals), bridging the gap between the classical Newtonian and the quantum
such as oxides, possessing a zero dimensionality [4]. world. In addition to this, metal clusters with small magnetic aniso-
tropy can be used as magnetic refrigerants, providing an efficient
alternative to the use of helium-3 [8–10], whereas in the field of
⇑ Corresponding author at: SSPC, Synthesis and Solid State Pharmaceutical bioinorganic chemistry, they have been studied, amongst others, as
Centre; School of Chemistry, National University of Ireland, Galway, Ireland.
models in order to elucidate details of the structure and function
E-mail address: [email protected] (C. Papatriantafyl-
lopoulou).

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0277-5387/Ó 2019 Elsevier Ltd. All rights reserved.
 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337 331

of the active center of several metalloenzymes, such as ferritin, the vial at room temperature. After 3 days, X-ray quality dark red
Mn4Ca water oxidizing complex in PSII, etc [11–14]. block-shaped crystals of 1 were collected by filtration, washed
Various synthetic approaches have now been developed for the with cold MeOH (2  2 mL) and dried under vacuum; the yield
synthesis of metal clusters [2], with the vast majority of them was 40%. The dried solid was analyzed satisfactorily as 1. Anal. Calc.
including the use of bridging ligand(s), as it does not only dictate for 1: C, 46.60; H, 3.91; N, 15.52. Found: C, 46.88; H, 3.52; N,
the metal topology and the molecular symmetry but also affects 15.64%. Selected IR data (KBr, cm1): m~ = 3400 (mb), 1624 (m),
the magnetic, electronic, optical, etc. properties of the cluster. 1608 (m), 1590 (w), 1510 (w), 1490 (s), 1410 (m), 1280 (m),
One family of ligands, that has been employed by us and others 1220 (m), 1190 (m), 1090 (s), 982 (m), 901 (m), 820 (m), 790
for the synthesis of new metal clusters, is the 2-pyridyl oximes (m), 700 (s), 650 (m), 623 (s), 570 (m), 501 (m).
(Scheme 1) [15–19]. The anions of such ligands are versatile and
lead to the isolation of various clusters with interesting properties 2.2.2. [Ni2Mn2{(py)C(Me)NO}6(OMe)2(MeOH)2](ClO4)2 (2)
in a variety of research objectives, including single molecule mag- This complex was prepared in the same manner as complex 1
netism, single-chain magnetism behaviour, etc. Our group recently but by increasing the quantity of Mn(ClO4)26H2O (0.362 g,
reported two multiple-decker Ni12 and Ni16 molecular ferromag- 1.00 mmol). Red prismatic crystals were formed within one day,
nets bearing the pyridine-2-aldoxime, that display high spin and these were collected by filtration, washed with cold MeOH
ground states S = 6 and S = 8, respectively, arising from ferromag- (2  2 mL) and dried under vacuum; the yield was 55%. The dried
netic exchange interaction between the octahedral NiII ions solid was hygroscopic and analyzed satisfactorily as 23H2O. Anal.
[20,21]. We decided to expand our research efforts exploring the Calc. for 23H2O: C, 38.99; H, 4.41; N, 11.86. Found: C, 39.42; H,
use of 2-pyridyl oxime ligands for the synthesis of mixed metal 4.01; N, 11.39%. Selected IR data (KBr, cm1): m~ = 3380 (mb),
Ni/Mn clusters. The magnetic coupling between NiII and MnIII is 1621 (m), 1583 (w), 1501 (w), 1478 (s), 1432 (m), 1296 (m),
stronger than that between MnII and MnIII, preventing complica- 1179 (m), 1112 (s), 989 (m), 908 (m), 813 (m), 776 (m), 708 (s),
tions from low-lying excited states in the analysis of the low-tem- 635 (m), 623 (s), 558 (m), 490 (m).
perature magnetic susceptibility data [22]. In addition, although
high nuclearity mixed-metal MnIII–NiII complexes are relatively 2.2.3. [Mn8O4(NO3)2{(py)C(ph)NO}8(HCO2)2(MeOH)2] (3)
rare, they have the potential to yield species with unusually high Method A: Ni(ClO4)26H2O (0.040 g, 0.10 mmol), (py)C(ph)NOH
nuclearities, such as the Mn36Ni4 ‘‘loop-of-loops-and-supertetrahe- (0.060 g, 0.30 mmol), Mn(NO3)26H2O (0.086 g, 0.30 mmol) and
dra” aggregate with S = 26 [23]. NaOMe (0.017 g, 0.30 mmol) were dissolved in CH2Cl2 (20 mL).
Herein, we report the synthesis and characterization of Ni2Mn The resultant yellowish solution was stirred for 24 h at room tem-
(1), Ni2Mn2 (2) and Mn8 (3) species from the employment of perature, during which time its color turned to dark brown/black.
methyl-2-pyridyl oxime (in 1 and 2) and phenyl-2-pyridyl oxime Subsequently, a small quantity of brown precipitate was removed
(in 3). 1 and 2 are the first examples of a 3d–3d0 heterometallic by filtration and the solution was layered with Et2O (40 mL). Slow
cluster bearing the methyl-2-pyridyl oxime; they exhibit antiferro- mixing gave well-formed, X-ray quality black crystals of the pro-
magnetic exchange interactions between the metal centers that duct, which were collected by filtration, washed with Et2O
leads to a diamagnetic ground state. (2  3 mL) and dried in air. Typical yields were in the 5–15% range.
Anal. Calc. for 3: C, 51.47; H, 3.64; N, 9.61. Found: C, 51.28; H, 3.87;
2. Experimental N, 10.11%. Selected IR data (KBr, cm1): m~ = 3445m, 2363m,
2344m, 1684m, 1653s, 1616w, 1508m, 1559s, 1453m, 1437m,
2.1. General and physical measurements 1384s, 1190w, 1100w, 1064m, 1029m, 791w, 744w, 709m,
600m, 462w.
All manipulations were performed under aerobic conditions Method B: Following the same procedure as in Method A, but in
using materials (reagent grade) and solvents as received. (py)C the absence of a NiII source, black, prismatic crystals of 3 were iso-
(Me)NOH was prepared as previously described [24]. lated in 12% yield. The product was identified by IR spectral com-
parison with the authentic material.

2.2. Compounds preparation

2.3. Physical studies

2.2.1. [Ni2Mn{(py)C(Me)NO}6](ClO4) (1)

Infrared spectra were recorded in the solid state (KBr pellets) on
Ni(ClO4)26H2O (0.366 g, 1.0 mmol), (py)C(Me)NOH (0.408 g,
a Shimadzu Prestige-21 spectrometer in the 4000–400 cm1 range.
3.0 mmol), Mn(ClO4)26H2O (0.145 g, 0.40 mmol) and NaOMe
Variable-temperature dc and ac magnetic susceptibility data were
(0.162 g, 3.0 mmol) were dissolved in MeOH (25 mL). The resultant
collected at the University of Florida using a Quantum Design
solution was stirred for 1 h at room temperature. Subsequently, a
MPMS-XL SQUID susceptometer equipped with a 7 T magnet and
small quantity of red precipitate was removed by filtration and
operating in the 1.8–300 K range. Samples were embedded in solid
the dark red filtrate was allowed to stand undisturbed in a closed
eicosane to prevent torquing. The ac magnetic susceptibility mea-
surements were performed in an oscillating ac field of 3.5 G and a
zero dc field. The oscillation frequencies were in the 5–1488 Hz
range. Pascal’s constants were used to estimate the diamagnetic
corrections, which were subtracted from the experimental suscep-
tibilities to give the molar paramagnetic susceptibility (vM).

2.4. Single-crystal X-ray crystallography

Data were collected at the University of Cyprus on an Oxford-

Diffraction Xcalibur-3 diffractometer, equipped with a CCD area
R=H, Me, Ph, NH2, CN... detector and a graphite monochromator utilizing Mo Ka radiation
(k = 0.71073 Å). Suitable crystals for 1–3 were attached to glass
Scheme 1. Structural formula of the family of 2-pyridyl oximes. fiber using paratone-N oil and transferred to a goniostat where
332 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337

they were cooled to 100 K for data collection. Empirical absorption in the reaction mixture, and following a similar procedure to the
corrections (multi-scan based on symmetry-related measure- one that yielded 1, compound [Ni2Mn2{(py)C(Me)NO}6(OMe)2
ments) were applied using CrysAlisRED software [25]. Software (MeOH)2](ClO4)2 (2) was formed in good yield. The stoichiometric
packages used: CrysAlisCCD for data collection, CrysAlisRED for cell reactions that afforded compounds 1 and 2 are summarized in
refinement and data reduction [25], SHELXL for structure solution Eqs. (1) and (2).
[25], WINGX for geometric calculations [26], while DIAMOND
[27] and MERCURY [28] were used for molecular graphics. The pro- 2NiðClO4 Þ2  6H2 O þ MnðClO4 Þ2  6H2 O þ 6ðpyÞCðMeÞNOH
gram Squeeze [29], a part of the PLATON package of crystallo- þ 5NaOMe þ 1=4O2
graphic software, was used to remove contribution of highly MeOH

! Ni2 MnfðpyÞCðMeÞNOg6 ðClO4 Þ þ5MeOH
disordered solvate molecules in 2 and 3. The non-H atoms were 1
treated anisotropically, whereas the H atoms were placed in calcu- þ 5NaClO4 þ 37=2H2 O ð1Þ
lated, ideal positions and refined as riding on their respective C
atoms.
Crystallographic data can be found in Table 1. 2NiðClO4 Þ2  6H2 O þ 2MnðClO4 Þ2  6H2 O þ 6ðpyÞCðMeÞNOH
þ 6NaOMe þ 1=2O2
MeOH

! Ni2 Mn2 fðpyÞCðMeÞNOg6 ðOMeÞ2 ðMeOHÞ2 ðClO4 Þ2
3. Results and discussion 2

þ 2MeOH þ 6NaClO4 þ 25H2 O ð2Þ

3.1. Synthesis
After the isolation of 1 and 2, which revealed that small changes
Our groups have developed an intense interest in the employ- in the NiII/MnII ratio yields different products, many other experi-
ment 2-pyridyl oximes as a means for the isolation of metal clus- ments were performed towards this direction. During these efforts,
ters [20,21,30–35]. Such ligands have a rich coordination it was observed that by further decreasing the amount of NiII in the
chemistry, bridging a large number of metals, thus resulting in reaction mixture, a dark brown/black microcrystalline precipitate
the formation of high nuclearity species, whereas they often favor was formed. Efforts were then took place to grow single crystals
the ferromagnetic coupling between the metal centers. Our by using different solvents, metal sources and bases; however, this
research efforts have yielded a variety of homometallic and 3d/4f was not feasible, so we decided to use (py)C(ph)NOH, hoping that
mixed-metal species, including Ni12 [20], Ni16 [20,21], Ni8Ln8 the additional p–p interactions introduced by the phenyl rings,
[31], etc, examples. Wishing to expand this work, we aimed at could potentially improve the crystallinity of the product. Indeed,
the investigation of the previously unexplored NiII/MnIII/(py)C the reaction of Ni(ClO4)26H2O, (py)C(ph)NOH, Mn(NO3)26H2O
(Me)NOH reaction system, probing its potential to yield new 3d– and NaOMe, in a 1:3:3:3 molar ratio, in CH2Cl2, gave dark brown
3d0 mixed-metal clusters with interesting structural features and crystals of the homometallic compound [Mn8O4(NO3)2{(py)C(ph)
magnetic properties. NO}8(HCO2)2(MeOH)2] (3) in a very low yield. After the determina-
Various reactions have been systematically explored in the tion of the crystal structure of 3, which revealed that the NiII ions
absence of carboxylates and other auxiliary ligands, with differing do not participate in its formation, the synthesis of 3 was achieved
reagent ratios, reaction solvents and other conditions. The reaction by reacting equivalent quantities of (py)C(ph)NOH, Mn(NO3)26H2-
of Ni(ClO4)26H2O, (py)C(Me)NOH, Mn(ClO4)26H2O and NaOMe, in O and NaOMe in CH2Cl2. Many experiments were also performed in
a 2:6:1:6 molar ratio, in MeOH, gave a dark red solution from order to improve the reaction yield; this has not been achieved,
which compound [Ni2Mn{(py)C(Me)NO}6](ClO4) (1) was subse- preventing the study of the magnetic properties of this compound.
quently isolated. Changing the molar ratio of the reactants to The synthesis of 3 is summarized in the stoichiometric Eq. (3). It is
1:3:1:3, i.e. increasing the quantity of the MnII ions that are present worth mentioning that a part of the MeO-ions, that were used to

Table 1
Crystallographic data for complexes 1, 2, and 3.

Complex 1 2 3
Empirical formula C42H42ClMnN12Ni2O10 C46H56Cl2Mn2N12Ni2O18 C100H80Mn8N18O24
Formula weight 1082.68 1363.23 2357.34
Crystal system trigonal triclinic monoclinic

Space group R-3 P1 C 2/c
a (Å) 14.1458(6) 9.1751(6) 24.8584(8)
b (Å) 14.1458(6) 12.4211(10) 16.5098(6)
c (Å) 23.9250(8) 14.2957(13) 26.3028(11)
a (°) 90.00 87.503(7) 90
b (°) 90.00 88.130(7) 95.279(4)
c (°) 120.00 79.355(6) 90
V (Å3) 4146.1(4) 1599.1(2) 10749.1(7)
Z 3 1 4
qcalc (g cm3) 1.301 1.416 1.457
Radiation, k (Å) 0.71073 0.71073 0.71073
l (mm1) 1.006 1.121 0.986
T (K) 100(2) 100(2) 100(2)
Measured/independent reflections (Rint) 11606/2301 (0.0182) 25161/6950 (0.0283) 29395/9152 (0.0699)
Parameters refined 143 405 688
Goodness of fit (GoF) (on F2) 1.084 1.036 1.066
R1a (I > 2r(Ι)) 0.0566 0.0376 0.0813
wR2b 0.1660 0.1087 0.2039
(Dq)max/(Dq)min (e Å3) 1.459/0.431 0.609/0.435 0.353/0.213
a
R1 = R(|Fo|  |Fc|)/R(|Fo|).
b
wR2 = {R[w(Fo2  Fc2)2]/R[w(Fo2)2]}1/2, w = 1/[r2(Fo2) + (aP)2 + bP], where P = (Fo2 + 2F2c )/3 and a and b are the two weighting parameters suggested by the SHELXL refinement
software.
 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337 333

deprotonate the ligand, have been oxidized to HCO 2 during the lengths [2.024 Å] being slightly shorter than the Νi–Νpy ones
aerial aggregation process [36] as small alkoxides are susceptible [2.060 Å]. The structural core of the complex can be described as a
to air oxidation [37]. linear heterometallic {Ni2Mn(N\O)6}+ unit, where the six diatomic
N\O bridges are coming from six different oximate groups. Alterna-
8MnðNO3 Þ2  6H2 O þ 8ðpyÞCðphÞNOH þ 14NaOMe þ 3O2 tively, the structure of 1 can be described as being constructed by
h i
CH2 Cl2
! MnII4 MnIII two [Ni{(py)C(Me)NO}3] fragments, which are linked to a central
4 O4 ðNO3 Þ2 fðpyÞCðphÞNOg8 ðHCO2 Þ2 ðMeOHÞ2
3
MnIII ion. This is a building block approximation and can be consid-
ered as a rational approach for interpreting, predicting and control-
þ 10MeOH þ 14NaNO3 þ 48H2 O ð3Þ
ling the rather ‘‘serendipitous” metal cluster’s assembly [38].
A principal C3 axis passes through the three metal ions in 1,
3.2. Description of structures while the MnIII is located on an inversion center. The NiII ions are
six-coordinate with distorted octahedral coordination sphere,
Representations of the molecular structures and structural which is completed by six N donor atoms, three pyridyl and three
cores of complexes 1–3, are shown in Figs. 1–3. Selected inter- oximic in facial (fac) arrangement. The coordination geometry
atomic distances and angles for the three complexes are listed in around the MnIII ion forms a nearly perfect octahedron with the
Tables 2–4. six Mn–O bonds being equivalent as a consequence of the crystal-
1 crystallizes in the trigonal space group R-3. Its crystal structure lographic symmetry in 1. Hence, 1 is a conceptual model for the
is composed of trinuclear [NiII2MnIII{(py)C(Me)NO}6]+ cations and Pearson’s Hard and Soft Acids and Bases (HSAB) theory, with the
ClO hard basic O donor atoms tending to coordinate to the higher oxi-
4 anions. The cationic complex possesses a C3i symmetry and con-
sists of two NiII and one MnIII ions that are held together through six dation MnIII species, while the intermediate basicity N atoms
g1:g1:g1:l2 (py)C(Me)NO ligands (Scheme 2) with the Ni–Nox bond showing a preference for the less acidic NiII ions.

Fig. 1. Representation of the molecular structure of the cationic cluster 1 (top) and its {Ni2Mn(N\O)6}+ structural core (bottom). Color code MnIII, blue; NiII, green; O, red; N,
aqua; C, grey. The hydrogen atoms and the ClO 4 counteranions have been omitted for clarity. (Colour online.)
334 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337

Fig. 2. Representation of the molecular structure of the cationic cluster 2 (top) and its structural core (bottom). Color code MnIII, blue; NiII, green; O, red; N, aqua; C, grey. The
hydrogen atoms and the ClO 4 counteranions have been omitted for clarity. (Colour online.)

The oxidation state of the MnIII ion was confirmed by charge ions consists of six N atoms, coming from three different
balance considerations and bond-valence sum (BVS) calculations (py)C(Me)NO ligands, whereas the coordination sphere of the MnIII
[39]. The intracationic intermetallic distances are Ni  Mn = 3.501 ions is completed by three oximate O atoms, two methoxide O atoms
(1) Å and Ni  Ni0 = 7.002(1) Å; a close inspection shows that there and one terminal MeOH. The intracationic, intermetallic distances
are not significant inter- or intracationic hydrogen bonding inter- are Ni  Mn = 3.489(1) Å, Mn–Mn0 = 3.006(1) Å, and Ni  Ni0 =
actions, and the cations are well-isolated with the shortest 9.611(1) Å; there are not strong inter- or intramolecular hydrogen
metal  metal separation between the neighboring Ni2Mn units bonding interactions in 2, and the shortest metal  metal distance
being 8.225(2) Å (Ni  Ni).  between the neighboring Ni2Mn2 cations is 8.484(2) Å (Ni  Mn).
Cluster 2 crystallizes in the triclinic space group P 1. Its struc- The oxidation states of the Mn and the protonation level of the
II III
ture consists of a centrosymmetric [Ni2 Mn2 {(py)C(Me)NO}6 O atoms were confirmed by charge balance considerations and
(OMe)2(MeOH)2]2+ cation, and two ClO 4 ions. The four metal ions bond-valence sum (BVS) calculations [39], as well as the observa-
are held together through six g1:g1:g1:l2 pyridyl oximate ligands tion of Jahn–Teller distortions for the octahedral MnIII ions, which
(Scheme 2), and two l-MeO bridging ligands. They display a zig- take the form of axial elongation of the O2–Mn–O3 and the sym-
zag arrangement with the two MnIII ions being located at the center metry equivalent axes.
and the NiII ions on the outer part. The structure of 2 can be 1 and 2 are the first 3d–3d0 mixed-metal clusters bearing the
described as consisting of [Ni{(py)C(Me)NO}3] fragments, neutral or anionic form of (py)C(Me)NOH. They also join a small
which are linked to a MnIII ion, constructing an heterometallic family of 2-pyridyl oximate Ni/Mn complexes, the vast majority
[(Ni{(py)C(Me)NO}3)Mn]2+ unit; the dimerization of the latter of which is based on 2-pyridyl aldoxime and its derivatives
through the l-MeO ions results in the formation of 2. [40–48].
All the metal ions in 2 ions display a distorted octahedral coordi- 3 crystallizes in the monoclinic space group C 2/c. Its structure
nation geometry. The coordination environment around the NiII consists of neutral [Mn8O4(NO3)2{(py)C(ph)NO}8(HCO2)2(MeOH)2]
 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337 335

Table 3
Selected interatomic distances (Å) and angles (°) for 2.

Interatomic distances (Å)

Ni–N1 2.097(2) Mn–O1 1.920(2)
Ni–N2 2.054(2) Mn–O2 2.173(2)
Ni–N3 2.101(2) Mn–O3 1.904(2)
Ni–N4 2.033(2) Mn–O4 2.288(2)
Ni–N5 2.117(2) Mn–O5 1.949(2)
Ni–N6 2.042(2) Mn–O50 1.946(2)
Ni–Mn 3.489(2) Mn–Mn0 3.006(2)
Bond angles (°)
N1–Ni–N2 77.2(1) O1–Mn–O2 95.7(1)
N1–Ni–N3 92.4(1) O1–Mn–O3 96.7(1)
N1–Ni–N4 99.5(1) O1–Mn–O4 85.7(1)
N1–Ni–N5 94.3(1) O1–Mn–O5 95.2(1)
N1–Ni–N6 159.7(1) O1–Mn–O50 171.2(1)
N2–Ni–N3 161.7(1) O2–Mn–O3 96.2(1)
N2–Ni–N4 89.3(1) O2–Mn–O4 169.2(1)
N2–Ni–N5 102.3(1) O2–Mn–O5 86.2(1)
N2–Ni–N6 87.2(1) O2–Mn–O50 90.4(1)
N3–Ni–N4 77.4(1) O3–Mn–O5 167.6(1)
N3–Ni–N5 93.4(1) O3–Mn–O50 89.0(1)
N3–Ni–N6 105.9(1) O3–Mn–O4 94.3(1)
N4–Ni–N5 93.2(1) O5–Mn–O50 78.7(1)
N4–Ni–N5 163.7(1) O4–Mn–O5 83.0(1)
N5–Ni–N6 76.1(1) O4–Mn–O50 87.2(1)
a
Symmetry transformations used to generate equivalent atoms: x, 1  y, 1 z.

Table 4
Selected interatomic distances (Å) and angles (°) for 3.

Interatomic distances (Å)

Mn1–O5 1.838(4) Mn  Mn20 3.260(4)
Mn1–O6 1.850(4) Mn1  Mn4 3.641(4)
Mn2–O5 1.868(4) Mn1  Mn3 3.343(4)
Mn2–O6 1.926(4) Mn2  Mn3 3.643(4)
Mn2–O60 2.311(5) Mn2  Mn4 3.403(4)
Mn3–O6 2.248(5) Mn3  Mn20 3.896(4)
Mn4–O5 2.071(4) Mn4  Mn20 5.545(4)
Mn1  Mn2 2.789(5)
Bond angles (°)
O5–Mn1–O6 85.1(2) Mn1–O6–Mn3 108.9(2)
O5–Mn2–O6 82.2(2) Mn1–O6–Mn20 111.6(2)
O5–Mn2–O60 111.0(2) Mn2–O5–Mn4 119.4(2)
Fig. 3. Representation of the molecular structure of the cationic cluster 3 (top) and O6–Mn2–O60 79.8(2) Mn2–O6–Mn3 121.3(2)
its structural core (bottom). Color code MnIII, blue; MnII, violet; O, red; N, aqua; C, Mn1–O5–Mn2 97.6(2) Mn2–O6–Mn20 100.2(2)
grey. The hydrogen atoms have been omitted for clarity. (Colour online.) Mn1–O5–Mn4 137.2(2) Mn3–O6–Mn20 117.4(2)
Mn1–O6–Mn2 95.2(2)
a
Symmetry transformations used to generate equivalent atoms: x + 1/2, y + 1/2,
Table 2 z + 1.
Selected interatomic distances (Å) and angles (°) for 1.

Interatomic distances (Å)

Ni–N1 2.080(3) Ni–N2B 2.015(3)
Ni–N1A 2.080(3) Mn–O1 1.930(2)
Ni–N1B 2.080(3) Mn–O1A 1.930(2)
Ni–N2 2.015(3) Mn–O1B 1.930(2)
Ni–N2A 2.015(3)
Bond angles (°)
N1–Ni –N1A 95.0(1) N2–Ni–N2A 87.1(1)
N1–Ni–N2 77.4(1) O1–Mn–O10 180.0(1)
N1–Ni–N2A 103.1(1) O1–Mn–O1A 94.6(1)
N1–Ni–N2B 160.8(1) O1–Mn–O1A0 85.4(1)
Scheme 2. The g1:g1:g1:l2 coordination mode of the organic ligands in 1, 2 (left),
Ni–Mn 3.501(1)
and 3 (right).
a
Symmetry transformations used to generate equivalent atoms: (A): x + y, x, z;
4 (l4-O)2(l3-O)2}
{MnII4MnIII 12+
(B): y, x  y, z; (0 ): x, y, 1 – z; (A0 ): x  y, x, 1  z; (B0 ): y, x + y, 1  z. metal core, which is composed of two
{Mn2 Mn2 (l4-O)(l3-O)} units linked through the two l4-O2 ions.
II III 6+

The peripheral ligation in 3 is completed by two chelate NO 3

cluster molecules. There are four MnII and four MnIII ions that are ions and two terminal MeOH molecules. All the metal ions are
held together through two l4-O2 and two l3-O2 ions, eight g1: six-coordinate displaying distorted octahedral geometry. The Mn
g1:g1:l2 (py)C(ph)NO ligands (Scheme 2), and two l2-HCO2 ions. oxidation states and the protonation level of the O2 ions were
The (py)C(ph)NO ligands connect either two MnIII, or one MnII confirmed by charge balance considerations and bond-valence
with one MnIII ions, whereas the HCO II
2 ions bridge two Mn metal sum (BVS) calculations [39], as well as the observation of Jahn–
centers in a syn-anti fashion. 3 possesses a double-butterfly Teller distortions at the MnIII ions.
336 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337

Closer inspection of the crystal structure of 3 reveals that there

are no strong inter- or intramolecular interaction thus, the Mn8
units are well-separated with the shortest metal  metal distance
between neighboring molecules in 3 being 10.008 Å (Mn3  Mn4).
3 is a new addition in the small family of high nuclearity Mn/
(py)C(ph)NO(H), which include Mn3, Mn4, Mn6, Mn8, Mn12 species
[45,49–55]; it is the only one, among the latter, that display a Scheme 3. Schematic representation of the coupling scheme used to model dc data
4 (l4-O)2(l3-O)2}
{MnII4MnIII 12+
double-butterfly structural core, for 2.
although this topology is known in 3d metal cluster chemistry.
 
3.3. Magnetism studies
H ¼ 2j ^S1  ^S2 þ ^S1  ^S20  2J 0 ^S2  ^S2 ð4Þ

The distance between the NiII ions in 1 is 7.0(2) Å, hence the J0

Solid state, variable-temperature magnetic susceptibility mea-
value is expected to be negligible and can be omitted from Eq.
surements were performed on vacuum-dried microcrystalline
(4); the Hamiltonian is then simplified to
samples of complexes 1 and 23H2O suspended in eicosane to pre-
 
vent torquing. The dc molar magnetic susceptibility (vM) data were H ¼ 2j ^S1  ^S2 þ ^S1  ^S20 ð5Þ
collected in the 5.0–300 K range in a 0.1 T (1000 Oe) magnetic field,
and are shown in Fig. 4 as vMT versus T plots. For 1, the vΜT stea- and its eigenvalues are given by Eq. (6), where ŜA = Ŝ2 + Ŝ20 , S1 = 2
dily decreases with decreasing temperature from 5.11 cm3 mol1 K and S2 = S20 = 1, and ST is the total spin of the whole molecule.
at 300 K to 2.73 cm3 mol1 K at 50 K and then drops rapidly to
0.71 cm3 mol1 K at 5.0 K. The vΜT at 300 K is very close to the EðST ; SA Þ ¼ J ½ST ðST þ 1Þ  SA ðSA þ 1Þ ð6Þ
spin-only (g = 2) value of 5.0 cm3 mol1 K expected for one MnIII Fitting of the experimental data for 1 to the corresponding Van
and two NiII non-interacting ions. For 23H2O, the vMT value at Vleck equation [56] gave the solid line in Fig. 4, with fit parameters
300 K is 7.54 cm3 K mol1, close to the calculated one (8.0 cm3 - J = 6.34 ± 0.14 cm1 and g = 2.09 ± 0.01, and a temperature-
mol1 K) for two MnIII and two NiII non-interacting ions and independent paramagnetism (TIP) term held constant at
decreases steadily with decreasing temperature to 0.56 cm3 - 300  106 cm3 mol1.
K mol1 at 5.0 K. Clearly, the profiles of the vMT versus T plots The magnetic properties of 23H2O are modeled by the Hamilto-
for 1 and 23H2O reveal the existence of antiferromagnetic interac- nian equation H = 2 J1 (Ŝ1Ŝ2 + Ŝ1Ŝ20 )  2 J2 Ŝ2Ŝ20 (7), according to
tions between the metal ions and an S = 0 ground state. Scheme 3. With this model and using the PHI software, the dc data
The isotropic Heisenberg spin Hamiltonian for the linear com- were simulated with the obtained converging parameters being
plex 1 is given by Eq. (4), where J is the NiII–MnIII and J0 the NiII–NiII J1 = 4.57 ± 0.08 cm1, J2 = 12.72 ± 0.12 cm1 and g = 2.18 ± 0.01
exchange interactions (Fig. 5): [57].
In order to independently probe the spin ground state value of 1
and 23H2O, alternating current (ac) magnetic susceptibility mea-
surements were performed in the 2–15 K temperature range in a
3.5 Oe ac field oscillating at 50–950 Hz. Ac susceptibility studies
are a powerful complement to dc studies for determining the
ground state of a system, because they preclude any complications
arising from the presence of a dc field. The v0 MT for both com-
pounds (Figs. S1 and S2 in Supplementary Material) decreases con-
tinuously with decreasing temperature, heading to zero 0 K,
confirming their diamagnetic ground state.

4. Conclusions

Two mixed-metal, [NiII2MnIII{(py)C(Me)NO}6](ClO4) (1) and

[Ni2 MnIII
II
2 {(py)C(Me)NO}6(OMe)2(MeOH)2](ClO4)2 (2), and one
homometallic, [MnII4MnIII
4 O4(NO3)2{(py)C(ph)NO}8(HCO2)2(MeOH)2]
(3), compounds have been synthesized by the employment of 2-pyr-
idyl oximes in Ni/Mn chemistry in the absence of auxiliary bridging
ligands. 1 and 2 possess a linear and zig-zag metal arrangement,
Fig. 4. vMT versus T plots for complexes 1 (j), and 23H2O (▲) in the temperature respectively, and are the first 3d–3d0 metal clusters, containing
range 5.0–300 K in 0.1 T applied dc field. The solid lines represent the fit of the data
to a theoretical expression; see the text for the fit parameters.
(py)C(Me)NOH. 3 displays a double-butterfly {MnII4MnIII 4 (l4-O)2(l3-
O)2}12+ structural core and joins the small family of Mn/(py)C(ph)
NO complexes [45,49–55]. It is noteworthy to mention that the
synthesis of 3 was inspired by the unsuccessful attempts to obtain
new products by using small amounts of Ni(II) in the reaction system
that gave compounds 1 and 2. 1 and 2 have a diamagnetic ground
state.
2-Pyridyl oximes have been extensively used in 3d and 3d-4f
metal cluster chemistry and yielded compounds with interesting
structures and extraordinary magnetic properties [20,21,30–35].
Their employment in 3d–3d0 metal chemistry, though, has not
been systematically investigated, and this work demonstrates its
Fig. 5. The exchange interactions in 1. potential to provide access to new compounds. We believe that
 C.G. Efthymiou et al. / Polyhedron 171 (2019) 330–337 337

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