A Pentanuclear Cobalt Complex with two [CoII(CH3O)3]– Units Wrapping a Triangular [CoIII3O]7+ Core: Synthesis, Structure, and Magnetic Properties

Article abstract of DOI:10.1002/zaac.201800138

The reaction of Hppko (Hppko = phenyl 2-pyridyl ketone oxime) and CoCl₂·6H₂O in the CH₃OH solvent with the presence of triethylamine (NEt₃) at room temperature and the exposure to air resulted in the formation of a new pentanuclear, mixed-valence cobalt complex with the molecular formula [{Co^II(CH₃O)₃}₂{Co^III₃(μ₃-O)(ppko)₃}Cl₂]. X-ray single crystal analysis displays a trigonal bipyramid configuration with the terminal two Co^II ions wrapping an triangle [Co^III₃O]⁷⁺ core. The intermolecular C–H···O and C–H···Cl interactions form a 2D network framework. The analysis of magnetic susceptibility revealed the dominant antiferromagnetic interactions and strong orbital contribution of Co^II ions.

Full text of DOI:10.1002/zaac.201800138

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201800138
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
A Pentanuclear Cobalt Complex with two [CoII(CH3O)3]– Units
Wrapping a Triangular [CoIII O]7+ Core: Synthesis, Structure, and
3
Magnetic Properties
Hua Yang,[a] Ruiling Li,[a] Dacheng Li,*[a] Suyuan Zeng,[a] and Jianmin Dou*[a]
Abstract. The reaction of Hppko (Hppko = phenyl 2-pyridyl ketone mid configuration with the terminal two CoII ions wrapping an triangle
oxime) and CoCl2·6H2O in the CH3OH solvent with the presence of [CoIII3O]7+ core. The intermolecular C–H···O and C–H···Cl interac-
triethylamine (NEt3) at room temperature and the exposure to air re-
tions form a 2D network framework. The analysis of magnetic suscep-
sulted in the formation of a new pentanuclear, mixed-valence cobalt tibility revealed the dominant antiferromagnetic interactions and strong
complex with the molecular formula [{CoII(CH3O)3}2{CoIII3(μ3-O)
orbital contribution of CoII ions.
(ppko)3}Cl2]. X-ray single crystal analysis displays a trigonal bipyra-
regarded as metal ions and nitrogen atoms replacing carbon
atoms of methylene carbons in crown ethers to display M–N–
O repeat units in MC rings. Following the different quantity
of M–N–O repeat units in MC rings, MCs have diverse struc-
tural types, such as 9-MC-3, 12-MC-4, 15-MC-5, 24-MC-8
and so on. In the trigonal-bipyramidal structures, the triangle
[M3O] units can act as 9-MC-3 structural type.[6] Meanwhile,
we found that many transition metal ions (Mn, Cu, Zn) and
3d-4f heterometallic ions have been involved in the formation
of MCs. However, it was limited for cobalt-oxime systems,
only including two 9-MC-3[6f,7] and one 12-MC-4 MCs.[8]
In our studies, we also explored various oxime ligands, and
reported several polynuclear complexes.[9] Recently, in view
of the studies of high-spin CoII (S = 3/2) complexes with
charming magnetic properties, such as antiferromagnetic,
ferromagnetic, spin frustration, SMMs and single ion
magnets (SIMs),[10–14] we still devote our effort to discuss the
syntheses of cobalt complexes with oxime ligands. Herein, we
Introduction
The construction of polynuclear transition metal complexes
has attracted considerable attention in the coordination chemis-
try field due to their interesting topology structures and diverse
magnetic properties, such as single molecule magnets (SMMs)
and single chain magnets (SCMs).[1.2] In these reported poly-
nuclear complexes, the involved bridging ligands consist of
carboxylates, Schiff base derivatives, alkoxides, and oximes.
However, the studies of such polynuclear complexes have re-
vealed that the pentanuclear complexes with trigonal-bipyram-
idal topology have been less documented.[3,4]
In the syntheses of the trigonal-bipyramidal structural com-
plexes, the pyrazole-based and triazole-based ligands were
found to play important roles. These trigonal-bipyramidal
complexes were also recognized as bis(triple-helical) cases, as
well as exhibiting specific properties, such as chirality, mag-
netic properties, and multiredox.[3] Unexpectedly, the salicyla-
doxime (H2salox) ligand also leaded to a trigonal bipyramid
represent
a pentanulear, mixed-valence cobalt complex
MnII2MnIII structure with a large magnetic anisotropy.[4] But
[{CoII(CH3O)3}2{CoIII3(μ3-O)(ppko)3}Cl2] (1). This complex
3
–
exhibits a trigonal-bipyramid structure with two {CoII(CH3O)3}2
such complexes did not display bis(triple-helical) configura-
tion. Therefore, to further investigate the pentanuclear trigonal-
bipyramidal complexes, it is necessary to choose the suitable
bridging ligands to prepare the target products.
units wrapping an triangle [CoIII3O]7+ core. Meantime, the
magnetic properties were also investigated.
Many oxime-metal complexes presented interesting metallic
macrocyclic structural feature, and the corresponding com-
plexes were named as metallacrowns (MCs),[5] which can be
Result and Discussion
The structure of Hppko ligand and its coordination mode
with central metal atoms are given in Scheme 1. Complex 1
¯
* Dr. D. Li
crystallizes in triclinic space group P1, and its crystal structure
is shown in Figure 1. The molecule contains two CoII ions, an
triangle [CoIII3O]7+ core, three ppko– ligands, six CH3O–
anions, and two coordinated Cl–. The triangle [CoIII3O]7+ core
consists of three cobalt ions (Co1, Co2, Co3) with a capping
μ3-O atom in the center. Two CoII ions (Co4 and Co5) wrap
the triangle [CoIII3O]7+ core with the help of six CH3O– anions
linking three CoIII to form a trigonal bipyramid configuration.
The Co4···Co5 distance is 4.945 Å. In the triangle core, the
E-Mail: Lidacheng62@163.com
* Prof. J. Dou
E-Mail: dougroup@163.com
[a] Shandong Provincial Key Laboratory of Chemical Energy Storage
and Novel Cell Technology
School of Chemistry and Chemical Engineering
Liaocheng University
252000, Liaocheng, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201800138 or from the au-
thor.
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Co–Co distances are 3.232 Å (Co1–Co2), 3.211 Å (Co2–Co3) tances of Co–Cl are 2.302 Å (Co4–Cl1) and 2.298 Å (Co5–
and 3.242 Å (Co1–Co3), and the Co–O–Co angles are 120.25° Cl2), respectively. For three ppko– ligands, the benzene ring
(Co1–O4–Co2), 118.92° (Co2–O4–Co3) and 120.59° (Co1– and pyridine ring of each ligand are not located in one plane
O4–Co3), respectively, approaching an equilateral triangle. with the twisting angles of 55.67, 67.99 and 57.21°, respec-
Thus, the whole molecule possesses a pseudo-C3 axis being tively. Furthermore, the inspection of the intermolecular inter-
perpendicular to the CoIII plane and passing through the ter- actions among complex 1 presents a 2D network arrangement
3
minal CoII ions and the central oxygen atom. The central O4 via the weak supermolecular C–H···O [the distances of 2.633 Å
III
atom is displaced 0.054 Å out of the mean Co3 plane, which (H2···O5), 3.485 Å (C2···O5)] and C–H···Cl [the distances of
is in accordance with the reported distances (0.50 and 3.730 Å (C11···Cl1), 3.602 Å (C22···Cl1) and 3.582 Å
0.493 Å).[6f,15] More interetingly, the molecule structure is chi- (C32···Cl2)] interactions (Figure 2a and b). The C–H···Cl inter-
¯
ral, but the complex crystallized in the P1 space group due to actions resulted in the formation of A and B chains, and the A
the presence of two molecules in one cell unit. The oxidation and B chains were linked together through C–H···O interac-
states of cobalt ions were determined through the bond lengths, tions. Thus, ABAB frameworks are presented in 2D network
charge balance, and bond-valence sum (Table S3, Supporting following the arrangement of complexes 1 with the interactions
Information).[16]
of C–H···O and C–H···Cl (Figure 3).
Scheme 1. The structure of Hppko ligand and coordination mode of
ppko–.
Figure 1. The asymmetric unit of complex 1. The hydrogen atoms are
omitted for clarity.
In the triangle core, three CoIII (Co1, Co2, and Co3) ions
adopt six-coordination octahedral geometry with coordination
atoms from two oximato N atoms and one oximato O atom of
two adjacent ppko– ligands, one μ3-O atom and two CH3O–
anions. Thus, three CoIII ions are bridged by three ppko–
groups along each edge of the triangle to display Co–N–O
repeat unit. The Co–N–O-Co torsion angles are 6.3° (Co1–
N2–O1–Co2), 6.2° (Co2–N4–O2–Co3), and 11.8° (Co3–N6–
Figure 2. Intermolecular C–H···O (a) interactions with the distances
2.633 Å (H2···O5), 3.485 Å (C2···O5) and C–H···Cl (b) interactions
with the distances 3.730 Å (C11–Cl1), 3.602 Å (C22–Cl1) and 3.582 Å
(C32–Cl2).
Thermogravimetric analysis (TGA) reveals that 1 displays a
O3–Co1), respectively, indicating the smaller twisting for N– weight loss of 12.2% between 120–160 °C, corresponding to
O bonds than that in the reported CoIII 9-MC-3 complex- the release of two coordinated Cl– anions. No further weight
es.[6f,15] Each apical CoII ions (Co4 and Co5) displays four- loss was observed below 400 °C, indicating good thermal sta-
coordination, tetrahedral coordination arrangements with four bility of 1. The powder X-ray diffraction (PXRD) demon-
coordination atoms supplied by three O atoms from three strates low purity for the samples obtained by evaporating sol-
CH3O– and one Cl–. The CoII complexes with tetrahedral coor- vent, compared with the simulated samples, which corresponds
dination environment also have been reported.[17] The dis- to the crystal samples.
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The fitting of magnetic susceptibility gives
J
=
–10.9 cm3·K·mol–1 and g = 2.19, suggesting the antiferromag-
netic interactions and strong orbital contribution of the CoII
ions.
Conclusions
A novel pentanuclear, mixed-valence cobalt complex was
successfully synthesized through CoCl2·6H2O and Hppko in
the presence of NEt3. Five Co ions were held together to exhi-
bit a trigonal bipyramid configuration with two CoII occupying
the apical positions and three CoIII ions residing in the equi-
lateral triangular plane. The magnetic susceptibility measure-
ments indicated the dominant antiferromagnetic coupling be-
tween two high-spin CoII ions, and the fitting of magnetic
susceptibility confirmed the strong orbital contribution of CoII
ions.
Figure 3. The polyhedral representation of the 2D network with
ABAB frameworks.
Experimental Section
The variable temperature DC magnetic susceptibility data
were collected in the temperature range of 1.8–300 K for the
powder samples. The plots of χMT vs. T and χM vs. T are
Materials and Instrumentation: All chemicals used in the experi-
mental process are commercially available and used as received with-
out further purification. Elemental analyses on C, H, and N were car-
ried out with an Elementar Vario EL analyzer. IR spectra were mea-
sured with a Perkin-Elmer Spectrometer. FT-IR spectra were recorded
with a Perkin-Elmer Spectrum BX spectrometer in KBr pellets. The
powder X-ray diffraction (PXRD) patterns were recorded with a
Bruker D8 Advance diffractometer with Cu-Kα radiation (λ =
1.5418 Å) at room temperature. Thermogravimetric analyses (TGA)
were performed in a nitrogen atmosphere with a heating rate of
10 K·min–1 with a Netzsch STA 449C thermal analyzer. The magnetic
susceptibility measurements were obtained with a Quantum Design
SQUID magnetometer MPMSXL in the temperature range of 1.8–
300 K and an applied field of 1 kOe. The mass of sample in the mag-
netic measurement for complex 1 was 9.73 mg.
–1
shown in Figure 4 (χM being the molar susceptibility). Because
CoIII ion is low-spin (t2g6, S = 0), the magnetic properties only
derive from two apical CoII ions of the triangle bipyramidal
mode. As seen from Figure 4, the χMT value at 300 K is
4.46 cm3·K·mol–1, significantly higher than the expected value
of 3.75 cm3·K·mol–1 for two non-interacting CoII ions with
g = 2.0. As decreasing temperature, the χMT values slightly
decreased, then sharply dropped to 0.58 cm3·K·mol–1 at 12 K
before increasing to a maximum of 0.76 cm3·K·mol–1. Further
cooling temperature, the value decreased to 0.38 cm3·K·mol–1
at 1.8 K, confirming a relative small, non-zero ground state.
This behavior of χMT clearly indicated the dominant antiferro-
magnetic interactions.[17] The decrease at low temperature was
attributed to zero-field splitting/weak intermolecular interac-
tions. Neglecting the effects of spin-orbit coupling, the pres-
ence of diamagnetic CoIII ions allows us to explore the Co–
Co magnetic coupling interactions. The magnetic susceptibility
equation is derived as:
Single-crystal X-ray Diffraction: The crystal structure of complex 1
was determined through single-crystal X-ray diffraction. The corre-
sponding data were collected with a Bruker Smart CCD area-detector
diffractometer with Mo-Kα radiation (λ = 0.71073 Å) by ω-scan mode
at room temperature. The program SAINT was used for integration of
the diffraction profiles, and the semi-empirical absorption corrections
were applied using SADABS.[18,19] All of the structures were solved
by direct methods using the SHELXS program of the SHELXTL pack-
age and refined by full-matrix least-squares methods with
SHELXL.[20] Metal ions were located from the E maps, and the other
non-hydrogen atoms were located in successive difference Fourier syn-
theses and refined with anisotropic thermal parameters on F2. Gen-
erally, hydrogen atoms bonded to carbon atoms were determined theo-
retically and refined with isotropic thermal parameters binding on their
parents. Hydrogen atoms of water and solvents were first located by
difference Fourier E maps and then treated isotropically as riding.
Crystallographic data (excluding structure factors) for the structure in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the de-
pository number CCDC-947001 (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
–1
Synthesis of Hppko: Hppko ligand was synthesized following the re-
Figure 4. The χMT and χM plots as functions of temperature (T) for
complex 1 at 1000 Oe.
ported procedure.[21] Phenyl-2-pyridone (17.2000 g, 0.10 mol) and hy-
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Journal of Inorganic and General Chemistry
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Chem. 2016, 55, 4891–4896; h) E. Gouré, B. Gerey, M. Cléman-
droxylamine hydrochloride (8.0600 g, 0.116 mol) were mixed in 6 mL
cey, J. Pécaut, F. Molton, J.-M. Latour, G. Blondin, M.-N. Col-
lomb, Inorg. Chem. 2016, 55, 9178–9186; i) V. Krewald, D. A.
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H2O with the flask placed in ice water. Afterwards, NaOH (9.2000 g,
0.23 mol) was added into the above solution in batches. After stirring
for 4 h in ice water, the solution was kept to stir for 40 h at room
temperature until the massive light pink precipitate was separated out.
The pH of the resulting precipitate in the ice water was changed to 5–
6 through adding HCl. The sample was filtered and dried with the
yield 78.69% (31.0000 g). M.p. 154–156°C. IR (KBr): ν˜ = 3437 (s),
3056 (w),1667 (s), 1579 (m), 1465 (w), 1446 (m), 1435 (m), 1385 (m),
1322 (m), 1303 (m), 1283 (m), 1241 (w), 1155 (m), 1094 (w), 1074
(w), 993 (m), 943 (m), 927 (w), 882 (w), 818 (w), 779 (m), 749 (m),
731 (w), 706 (s), 651 (m), 616 (m), 543 (w) cm–1. C12H10N2O: calcd.
C 72.73, H 5.05, N 10.03%; found C 72.65, H 5.21, N 10.35%.
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Synthesis of [{CoII(CH3O)3}2{CoIII3(μ3-O)(ppko)3}Cl2]: Hppko
(0.0990 g, 0.5 mmol) and CoCl2·6H2O (0.1190 g, 0.5 mmol) were
mixed in MeOH (20 mL). NEt3 (1 mmol) was added to the resulting
mixture with stirring for 6 h. Afterwards, the mixture was filtered, and
the filtering solution was left to stand out at air. The red crystals were
obtained after six weeks. Yield: 53% (based on Co). IR (KBr): ν˜ =
3439 (mb), 3054 (w), 1640 (m), 1589 (w), 1556 (w), 1462 (s), 1432
(w), 1379 (m), 1365 (s), 1198 (s), 1097 (s), 1046 (m), 948 (w), 899
(m), 804 (m), 708 (s), 645 (s), 623 (w), 569 (s), 512 (m), 454 (m) cm–1.
C42H45Cl2Co5N6O10: calcd. C 43.51, H 3.91, N 7.25%; found C 43.69,
H 3.65, N 7.13%.
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Supporting Information (see footnote on the first page of this article):
Tables showing Crystallographic data and structure refinement details,
Selected bond distances and angels, as well as the oxygen state of Co
ions (Tables S1-S3); Figures showing the TGA curve and PXRD pat-
terns (Figures S1-S2).
Acknowledgements
[10] a) Z. Q. Jia, X. J. Sun, L. L. Hu, J. Tao, R. B. Huang, L. S. Zheng,
Dalton Trans. 2009, 32, 6364–6367; b) S. D. Han, Y. Q. Chen,
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We greatly acknowledge financial supports from National Natural Sci-
ence Foundation of China (Grant 21671093, 21701078 and 21271097).
Keywords: Phenyl 2-pyridyl ketone oxime; Mixed-valence
cobalt; Synthesis; Structure elucidation; Magnetic properties
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Received: April 10, 2018
Published online: ᭿
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
H. Yang, R. Li, D. Li,* S. Zeng, J. Dou* ......................... 1–6
A Pentanuclear Cobalt Complex with two [CoII(CH3O)3]–
Units Wrapping a Triangular [CoIII3O]7+ Core: Synthesis,
Structure, and Magnetic Properties
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© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim