Copper(II) clusters of two pairs of 2,3-dihydroxybutanedioyl dihydrazones: Synthesis, structure, and magnetic properties

Article abstract of DOI:10.1002/ejic.201402784

Condensation reactions of (2R,3R)- and (2S,3S)-2,3-dihydroxybutanedihydrazide with salicylaldehyde and 3-methoxysalicylaldehyde gave two enantiomeric pairs, (2R,3R)/ (2S,3S)-2,3-dihydroxybutanedioylbis(salicylaldehydehydrazone) [(2R,3R)-BSH and (2S,3S)-BSH] and (2R,3R)/(2S,3S)-2,3- dihydroxybutanedioyl bis(3-methoxysalicylaldehydehydrazone) [(2R,3R)-MBSH and (2S,3S)-MBSH]. Their reactions with CuII salts provided two chiral hexanuclear clusters [Cu6L2(C5H5N)10]2[C5H6N]3(ClO4)7.(CH3OH).(C5H5N) [L = (2R,3R)-BSH; (2S,3S)-BSH] and four chiral tridecanuclear clusters [Cu13L3(OH)2(CH3COO)6(C5H5N)6(DMF)3].6DMF. 3H2O [L = (2R,3R)-BSH; (2S,3S)-BSH] and [Cu13X3(OH)2-(CH3COO)6(C5H5N)2(DMF)8].6H2O [X = (2R,3R)-MBSH, (2S,3S)-MBSH]. Their structures were determined by singlecrystal X-ray diffraction analysis. All six compounds are enantiomers of each other. The two hexanuclear clusters exhibit two orthogonal linear trinuclear units. The two pairs of tridecanuclear clusters display esthetic structures with different symmetries; they feature rare heptanuclear vertexsharing dicubane cores and their six unshared CuII vertexes are linked to another six CuII ions. These represent the first examples of chiral clusters bearing dicubane cores. Magnetic studies revealed the presence of overall antiferromagnetic interactions in these compounds.

Full text of DOI:10.1002/ejic.201402784

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DOI:10.1002/ejic.201402784
Copper(II) Clusters of Two Pairs of 2,3-Dihydroxy-
butanedioyl Dihydrazones: Synthesis, Structure, and
Magnetic Properties
Zilu Chen,[a] Suping Zhou,[a] Yanling Shen,[a] Huahong Zou,[a]
Dongcheng Liu,[a] and Fupei Liang*[a,b]
Keywords: Cluster compounds / Copper / Magnetic properties / Chirality / Structure elucidation
Condensation reactions of (2R,3R)- and (2S,3S)-2,3-dihyd-
(CH3COO)6(C5H5N)2(DMF)8]·6H2O [X
=
(2R,3R)-MBSH,
roxybutanedihydrazide with salicylaldehyde and 3-methoxy- (2S,3S)-MBSH]. Their structures were determined by single-
salicylaldehyde gave two enantiomeric pairs, (2R,3R)/
(2S,3S)-2,3-dihydroxybutanedioylbis(salicylaldehydehydraz-
one) [(2R,3R)-BSH and (2S,3S)-BSH] and (2R,3R)/(2S,3S)-2,3-
crystal X-ray diffraction analysis. All six compounds are
enantiomers of each other. The two hexanuclear clusters ex-
hibit two orthogonal linear trinuclear units. The two pairs of
dihydroxybutanedioyl bis(3-methoxysalicylaldehydehydraz- tridecanuclear clusters display esthetic structures with dif-
one) [(2R,3R)-MBSH and (2S,3S)-MBSH]. Their reactions
ferent symmetries; they feature rare heptanuclear vertex-
sharing dicubane cores and their six unshared CuII vertexes
are linked to another six CuII ions. These represent the first
examples of chiral clusters bearing dicubane cores. Magnetic
studies revealed the presence of overall antiferromagnetic
interactions in these compounds.
with CuII salts provided two chiral hexanuclear clusters
[Cu6L2(C5H5N)10]2[C5H6N]3(ClO4)7·(CH3OH)·(C5H5N) [L
=
(2R,3R)-BSH; (2S,3S)-BSH] and four chiral tridecanuclear
clusters [Cu13L3(OH)2(CH3COO)6(C5H5N)6(DMF)3]·6DMF·
3H2O [L = (2R,3R)-BSH; (2S,3S)-BSH] and [Cu13X3(OH)2-
chiral magnetic clusters are much less reported.[3a,3b,7] Thus,
we took on the challenge to develop more chiral magnetic
clusters by using new chiral ligands with the aim of explor-
ing esthetic cluster structures and their magnetic properties.
As is well known, magnetic cubane clusters have drawn
significant interest in the last years for their interesting
structures and their special magnetic properties. A few
groups have reported some homometallic and hetero-
metallic cubane clusters with special magnetic properties,
including single-molecular magnets.[8] However, most of
these studies revolve around single cubane structures and
defective dicubane structures;[9] perfect dicubanes such as
vertex-sharing dicubanes, face-sharing dicubanes, and edge-
sharing dicubanes are much less reported.[10] To the best of
our knowledge, there are only a few compounds possessing
the vertex-shared dicubane core, the magnetochemical
properties of which have been fully elucidated.[11] On the
other hand, only a few reports pertain to chiral paramag-
netic transition-metal clusters containing cubane struc-
tures.[4b,7a,12] The introduction of chirality into dicubane
structures has never been documented. The selection of
linking atoms is of great importance in controlling the
structures and properties of dicubanes. In this study, we
used alkoxo O atoms as linking atoms to consolidate metal
ions to form cubane structures that show magnetic interac-
tions. To achieve the targeted aim of obtaining discrete
polynuclear compounds, we used phenyl groups to control
the growth of the dimensionalities.
Introduction
The development of multifunctional materials in which
compounds combine different physical properties and func-
tions is appealing, and as such, chiral magnets have received
significant attention in recent years owing to the potential
synergy between structural chirality and magnetic proper-
ties in these compounds and the thus-derived novel func-
tionalities.[1] As demonstrated in recent studies, the intro-
duction of chirality into magnetic systems can result in
interesting properties such as magneto-optical properties,
ferroelectricity, and magnetochiral dichroism, all as a result
of the asymmetric dipole moment.[1a,2] A few examples in
which chirality was introduced in special magnetic materials
such as single-molecular magnets have been successful.[3]
The chirality in these chiral magnets can be induced by chi-
ral linkers[4] as well as by achiral linkers through spontane-
ous resolution with or without the aid of a chirality-in-
ducing agent.[3a,3c,5] However, most studies in this field are
centered around 1D to 3D compounds,[2b,6] and discrete
[a] School of Chemistry and Pharmaceutical Sciences, Guangxi
Normal University,
Guilin 541004, P. R. China
E-mail: fliangoffice@yahoo.com
http://www.ce.gxnu.edu.cn/chem/InfoShow.asp?id=330
[b] College of Chemistry and Bioengineering, Guilin University of
Technology,
Guilin 541004, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402784.
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On the basis of the above considerations, we prepared
two pairs of multifunctional chiral ligands and separated
two chiral hexanuclear clusters and four chiral tridecanu-
clear clusters. The four tridecanuclear clusters feature rare
heptanuclear vertex-sharing dicubane cores. They represent
the first examples in which chirality is introduced into dicu-
banes.
Results and Discussion
Synthesis and Characterization
(2R,3R)/(2S,3S)-2,3-Dihydroxybutanedihydrazide were
prepared from the reactions of diethyl (2R,3R)/(2S,3S)-2,3-
dihydroxybutanedioate with hydrazine hydrate following a
procedure described in the Supporting Information. Their
respective reactions with salicylaldehyde and 3-methoxysali-
cylaldehyde gave two enantiomeric pairs (2R,3R)/(2S,3S)-
2,3-dihydroxybutanedioylbis(salicylidenehydrazone)
[(2R,3R)-BSH and (2S,3S)-BSH] and (2R,3R)/(2S,3S)-2,3-
dihydroxybutanedioylbis(3-methoxysalicylidenehydrazone)
[(2R,3R)-MBSH and (2S,3S)-MBSH] as shown in
Scheme 1. Details of their synthesis and characterization
can be found in the Supporting Information. Reactions of
CuII salts with these chiral ligands by using similar tradi-
tional solution methods gave two chiral hexanuclear
Scheme 1. Synthetic routes to the chiral ligands used in this study.
clusters
[Cu6L2(C5H5N)10]2[C5H6N]3(ClO4)7·(CH3OH)·
(C5H5N) [L = (2R,3R)-BSH, 1; (2S,3S)-BSH, 2] and four corresponding pairs of compounds are enantiomers of each
chiral tridecanuclear clusters [Cu13L3(OH)2(CH3COO)6- other.
(C5H5N)6(DMF)3]·6DMF·3H2O [L = (2R,3R)-BSH, 3;
As revealed by single-crystal X-ray diffraction analysis,
(2S,3S)-BSH, 4] and [Cu13X3(OH)2(CH3COO)6(C5H5N)2- [Cu6{(2R,3R)-BSH}2(C5H5N)10]2[C5H6N]3(ClO4)7·CH3OH·
(DMF)8]·6H2O [X = (2R,3R)-MBSH, 5; (2S,3S)-MBSH, 6]. C5H5N (1) and [Cu6{(2S,3S)-BSH}2(C5H5N)10]2[C5H6N]3-
Compounds 1 and 2 were separated from the mixtures by (ClO4)7·CH3OH·C5H5N (2) are enantiomers that feature
using Cu(ClO4)2·6H2O as the CuII salt. However, replace- discrete hexanuclear units as shown in Figure 1. All of the
ment of Cu(ClO4)2·6H2O by [Cu2(OAc)4(H2O)2] in these re- CuII ions in 1 and 2 have square-pyramidal coordination
actions produced discrete tridecanuclear clusters 3–6. environments. The basal positions of Cu3–Cu6 are occu-
Clearly, the anions of the CuII salts contribute significantly pied by one pyridyl nitrogen atom, one phenolic oxygen
to the construction of the different types of clusters. The atom, one nitrogen atom of the C=N group, and one carb-
selection of pyridine/pyrazine as the base for 3–6 and only onyl oxygen atom; the apex position is open for another
pyridine for 1 and 2 is also of importance for the construc- pyridyl nitrogen atom. Cu1 and Cu2 are coordinated by one
tion of these compounds. All attempts to use inorganic pyridyl nitrogen atom, two carbonyl amide nitrogen atoms
bases or other organic bases in these reactions failed. Upon from two BSH5– ligands, and one alkoxo oxygen atom in
exposing crystals of 3–6 to air for longer than 3 h, the faces the basal positions; another alkoxo oxygen atom from an-
of the crystals became opaque and cracking was observed; other BSH5– ligand is in the apex position.
this implies the loss of lattice solvent molecules, as well as
The two BSH5– ligands in compounds 1 and 2 act as
the possible collapse of the skeleton. To further confirm pentavalent μ4,η10-bridging anions, and all of the nitrogen
this, the powder X-ray diffraction (PXRD) patterns of 3, as and oxygen atoms in the ligands are involved in coordina-
an example of these compounds, were recorded at different tion to the CuII ions as depicted (Figure 1, c,d). Among the
times (Figure S1, Supporting Information). Weakened in- six CuII ions, Cu1 and Cu2 are both chelated by two BSH5–
tensities and broadened peaks were observed in the PXRD ligands; however, the other CuII ions are only chelated by
patterns of 3 recorded after its exposure to air for longer one BSH5– ligand. Cu3, Cu1, and Cu4 are connected by
than 3 h.
two –N–N– groups from two BSH5– ligands to form a lin-
The chiralities of 1–6 were substantiated by circular di- ear trinuclear unit, as are Cu5, Cu2, and Cu6. Cu1 and Cu2
chroism (CD) spectroscopy, which was performed in the so- from the two linear trinuclear units are further bridged by
lid state at room temperature (Figure S2). The CD spectra two O–C–C–O moieties from two BSH5– ligands, which re-
of 1/2, 3/4, and 5/6 present Cotton effects, and the spectra sults in the consolidation of the six CuII ions by two BSH5–
of the compounds forming a pair are almost mirror images, ligands to form hexanuclear units in 1 and 2. The two linear
which indicates that each compound is enantiopure and the Cu3 units in the hexanuclear units are nearly normal to
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Figure 1. Molecular structures of (a) 1 and (b) 2 with selected atoms labeled and ligand coordination modes of (c) 1 and (d) 2.
each other with an angle of 86.97(1)° for 1 and 87.07(1)°
The unshared six CuII ions in the heptanuclear vertex-
for 2. To the best of our knowledge, this kind of hexanu- sharing dicubane cores of 3 and 4 are further linked to an-
clear cluster with two orthogonal linear trinuclear units is other six CuII ions (Cu1, Cu1A, Cu1B, Cu5, Cu5A, and
rare. Only one compound has been reported to possess this Cu5B) by the three BSH6– ligands to form discrete tridecan-
kind of skeleton.[13] The other reported hexanuclear clusters uclear units. Cu1 is coordinated by one carbonyl oxygen
with two linear trinuclear units usually exhibit “dimer-of- atom, one nitrogen atom and a phenoxyl oxygen atom from
trimers” structure with a ladder-like architecture.[13,14]
one BSH6– ligand, and another pyridyl nitrogen atom to
The single-crystal X-ray diffraction analysis results reveal form a planar square geometry. Cu5 has a square pyramidal
that 3 and 4 have the formula of [Cu13L3(OH)2(CH3COO)6- geometry in which the coordinating atoms in the basal posi-
(C5H5N)6(DMF)3]·6DMF·3H2O [L = (2R,3R)-BSH, 3; tions are similar to those in Cu1. The difference between
(2S,3S)-BSH, 4]; their tridecanuclear units are shown in Cu5 from Cu1 is that one of the axial positions of Cu5 is
Figure 2. The tridecanuclear units in 3 and 4 feature a dicu- coordinated by one DMF molecule. The pyridyl plane of
bane core with a threefold axis passing through the O12, Cu1 nearly parallels the phenyl plane of Cu5A with a dihe-
Cu3, and O13 atoms. The seven CuII ions in the dicubane dral angle of 2.377° for 3 and 1.068° for 4 and a center-to-
core are connected by two hydroxy groups and six alkoxo center distance of 3.8304(3) Å for 3 and 3.8126(2) Å for 4;
oxygen atoms from three BSH6– ligands to form a heptanu- this is indicative of the existence of π···π stacking interac-
clear vertex-sharing dicubane core; the six unshared CuII tions between the two rings. As a result, the two square
ions are arranged in a nearly eclipsed fashion (Figure 2). planes of Cu1 and Cu5A are nearly parallel to each other
Cu2, Cu2A, and Cu2B in one cubane are additionally con- with a dihedral angle of 7.183° for 3 and 7.785° for 4.
nected by three carboxylato groups in turn. The other three
Structural analysis revealed discrete tridecanuclear units
carboxylato groups in the dicubane core chelate separately in [Cu13X3(OH)2(CH3COO)6(C5H5N)2(DMF)8]·6H2O [X =
to Cu4, Cu4A, and Cu4B. The CuII ions in the dicubane (2R,3R)-MBSH, 5; (2S,3S)-MBSH, 6], as depicted in Fig-
core present three types of coordination geometries. Cu3 ure 3. The tridecanuclear units feature a heptanuclear ver-
possesses a nearly ideal trigonal prismatic geometry, as tex-sharing dicubane core with a twofold rotation axis de-
demonstrated by the twist angle [2.24(1)° for 3 and 2.42(1)° fined by Cu1 and the center of Cu3 and Cu3A. Four CuII
for 4] of the two triangular faces O3–O3A–O3B and O4– ions are bridged by three alkoxo oxygen atoms and one hy-
O4A–O4B, which was calculated as the mean of the New- droxy group to form one cubane. The two cubanes in 5 and
man projection angles viewed along the centroids of focus. 6 share one CuII vertex to form a heptanuclear vertex-shar-
This kind of ideal trigonal prism around the CuII ion is ing dicubane core; the six unshared CuII ions are arranged
unusual and unprecedented. The Cu2, Cu2A, and Cu2B in a nearly eclipsed fashion, which is similar to the arrange-
atoms have distorted octahedral coordination environments ments in 3 and 4. An important difference is that the dicub-
with one acetato oxygen atom, one hydroxy oxygen atom, ane cores in 5 and 6 show lower symmetry and slightly
and one alkoxo oxygen atom and one nitrogen atom from more severe distortion than those in 3 and 4, as indicated
one BSH6– ligand in the equatorial positions; another alk- by the corresponding Cu–O bond lengths and the O–Cu–O
oxo oxygen atom from another BSH ligand and another and Cu–O–Cu angles. Two of the CuII ions in each cubane
acetato oxygen atom are in the axial positions. Cu4, Cu4A, are further connected by one carboxylato group. Cu1 is co-
and Cu4B present coordination geometries similar to those ordinated by six alkoxo oxygen atoms to form a nearly ideal
of Cu2, Cu2A, and Cu2B. The Cu–O/N bond lengths are trigonal prismatic geometry, as demonstrated by the twist
comparable to those reported in the literature.[15]
angle [2.14(2)° for 5 and 2.01(2)° for 6] of the two triangular
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Figure 2. Molecular structures of (a) 3 and (b) 4 with selected atoms labeled. The dicubane cores in (c) 3 and (d) 4 (d). Ligand coordination
modes of (e) 3 and (f) 4. Symmetry codes for 3: A) –x + y, –x + 1, z; B) –y + 1, x – y + 1, z. Symmetry codes for 4: A) –x + y + 1, –x
+ 1, z; B) –y + 1, x – y, z.
faces O4–O5A–O12 and O4A–O5–O12A, which was calcu-
The dicubane cores in 5 and 6 are further connected to
lated as the mean of the Newman projection angles viewed another six CuII ions (Cu3, Cu3A, Cu6, Cu6A, Cu7, and
along the centroids of focus. This kind of ideal trigonal Cu7A) by the three MBSH6– ligands. Cu3 and Cu3A pres-
prism around the CuII ion is unusual and unprecedented. ent square pyramidal geometries. Their basal positions are
Cu4 presents a severely distorted octahedral geometry with occupied by one carbonyl oxygen atom, one N atom and
one alkoxo oxygen atom and one nitrogen atom from one one phenolic O atom from one MBSH6– ligand, and an-
MBSH6– ligand, one hydroxy group, and one DMF mol- other oxygen atom from one DMF. Their apex position is
ecule in the equatorial sites; one alkoxo oxygen atom and occupied by another weakly bound oxygen atom from one
one acetato oxygen atom sit in the axial positions. Cu2 is DMF molecule with much longer Cu–O bond lengths of
coordinated in a square pyramidal geometry with one 3.04(4) Å for 5 and 2.866(17) Å for 6. The two basal planes
hydroxy group, one alkoxo oxygen atom and one nitrogen of Cu3 and Cu3A are nearly parallel to each other with
atom from one MBSH6– ligand, and one acetate oxygen dihedral angles of 1.552(2)° for 5 and 3.038(8)° for 6 and
atom in the basal positions; another alkoxo oxygen atom Cu···Cu distances of 4.2583(13) Å for 5 and 4.2681(14) Å
sits in the apex position. Cu5 has a severely distorted octa- for 6. Cu6 and Cu6A present coordination geometries that
hedral geometry with one hydroxy group, one alkoxo oxy- are similar to those of Cu3 and Cu3A; one pyridyl N atom
gen atom and one nitrogen atom from the MBSH6– ligand, lies in one basal position instead of one oxygen atom from
and an acetato oxygen atom in the equatorial positions; an- one DMF molecule. The difference in the coordination geo-
other alkoxo oxygen atom and another carboxylato oxygen metries of Cu7 and Cu7A from those of Cu3 and Cu3A is
atom lie in the axial positions. The Cu–O/N bond lengths that there are no coordinating atoms in the axial positions.
are comparable to those in 3 and 4.
Thus, Cu7 and Cu7A show square planar geometries. The
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Figure 3. Molecular structures of (a) 5 and (b) 6 with selected atoms labeled. The dicubane cores of (c) 5 and (d) 6 and the ligand
coordination modes of (e) 5 and (f) 6. Symmetry codes for 5: A) –x + 2, y, –z + 1/2. Symmetry codes for 6: A) –x, y, –z + 3/2.
two basal planes of Cu6 and Cu7A (or Cu6A and Cu7) are (Scheme S1). This leads to corresponding O–C–C–O tor-
nearly parallel to each other with dihedral angles of sion angles in the range of 60.5(8) to 63.5(8)° for 1 and 2,
9.952(7)° for 5 and 6.442(6)° for 6 and Cu···Cu distances of and of 35.4(8) to 36.5(7)° for 3 and 4. The MBSH6– ligands
4.3786(11) Å for 5 and 4.4037(13) Å for 6. The pyridyl ring in 5 and 6 adopt coordination modes similar to those in 3
of Cu6 is nearly parallel to the phenyl ring of Cu7A with a and 4, and the corresponding O–C–C–O torsion angles are
dihedral angle of 8.238(7)° for 5 and 6.650(7)° for 6, a cen- in the range of 29.3(3) to 40(3)°. Compounds 3–6 show sim-
ter-to-center distance of 4.336(1) Å for 5 and 4.402(1) Å for ilar tridecanuclear skeletons and feature heptanuclear ver-
6, and a pyridyl center-to-phenyl plane distance of tex-sharing dicubane cores (Scheme 2). However, the tride-
3.566(1) Å for 5 and 3.521(1) Å for 6, which is indicative of canuclear units in 3 and 4 have threefold rotation axes, and
the existence of π···π stacking interactions between the two the tridecanuclear units in 5 and 6 have only twofold rota-
rings. All MBSH6– ligands in 5 and 6 behave in the same tion axes. In comparison to the BSH6– ligand in 3 and 4, the
coordination modes as those shown in Figure 3.
MBSH6– ligand in 5 and 6 has one more methoxyl group
The BSH ligand in 1 and 2 presents a μ4,η10-bridging on each phenyl group. It seems that the introduction of a
mode, which is much different from the μ7,η14-bridging methoxyl group into the ligand does not have a large in-
mode for the BSH ligand in 3 and 4. It is easy to see that fluence on the structures of the thus-formed complexes, but
the coordination modes for the two hydrazone parts at the it does reduce the symmetry of the structure. This kind of
two ends of the BSH ligand in 1–4 are the same heptanuclear vertex-sharing dicubane core having six un-
(Scheme S1). However, the two adjacent alkoxo O atoms in shared metal vertexes that are connected to another six
the middle part of the BSH ligand in 3 and 4 show coordi- metal ions has never been documented. To the best of our
nation modes that are much different to those in 1 and 2 knowledge, only a few paramagnetic metal compounds have
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been reported to show a heptanuclear vertex-sharing dicub- approximation to estimate the intertrimer and interhexamer
ane core.[11d–11g] Among them, only one CuII compound interaction (2zJЈ).
was reported with a heptanuclear vertex-sharing dicubane
core.[11d] However, this dicubane core is Cu7O6Cl2 not
Cu7O8. Furthermore, only a few chiral paramagnetic
clusters containing cubane structures have been report-
ed.[4b,7a,12] For the introduction of chirality into dicubane
(1)
structures, compounds 3–6 are the first examples.
Scheme 2. The dicubane cores in 3–6.
Figure 4. Plots of χm and χmT versus T for 1 and 2. The solid lines
denote the theoretical fits of the experimental data.
Magnetic Properties
As revealed by single-crystal X-ray diffraction analysis,
The magnetic susceptibility data of 1 and 2 were least-
squares fit to Equation (2) to give the best-fitting param-
eters: J = –59.45 cm–1, 2zJЈ = –0.74 cm–1, and g = 2.25 with
an agreement factor R = 1.22ϫ 10–4 for 1; and J =
–61.04 cm–1, 2zJЈ = –0.81 cm–1, and g = 2.28 with an agree-
ment factor R = 1.80ϫ 10–4 for 2. The fitting values agree
well with the experimental data (Figure 4). These results
indicate the presence of an overall intermetallic antiferro-
magnetic coupling in 1 and 2.
compounds 1/2, 3/4, and 5/6 are enantiomers of each other;
1 and 2 possess hexanuclear cluster skeletons, whereas 3–6
possess tridecanuclear cluster structures. Consequently, 1
and 2 might possess similar magnetic properties, as might
compounds 3–6; this was confirmed by solid-state magnetic
susceptibility (χm) measurements in the temperature range
of 2.0 to 300 K in a direct current field of 1000 Oe (see
Figures 4–6).
The magnetic properties of 1 and 2 in the form of both
χmT and χm versus T plots are shown in Figure 4. The χmT
values of 1 and 2 at 300 K are 2.08 and 2.14 cm3 Kmol–1
per Cu6 unit, respectively, which are close to the expected
value (2.25 cm3 Kmol–1) for six magnetically isolated high-
spin CuII ions. Upon decreasing the temperature, the χmT
(2)
As shown in Figures 5 and 6, the shapes of the χm and
values of 1 and 2 decrease steadily; this suggests the pres- χmT versus T curves for 3–6 are similar. The χmT values
ence of dominant antiferromagnetic coupling in the two of 3–6 at 300 K are 3.90, 3.79, 3.30, and 3.21 cm3 Kmol–1,
compounds. The plateau in the temperature range of 6 to respectively, which are lower than the value expected
40 K for both compounds might be caused by the net spins (4.88 cm3 Kmol–1) for 13 magnetically isolated high-spin
of the hexanuclear units.[16] The further steep decrease in CuII ions. Upon decreasing the temperature, the χmT values
χmT upon lowering the temperature could result from inter- decrease slowly and reach 1.25, 1.14, 0.87, and
hexanuclear antiferromagnetic interactions in 1 and 2. As 1.05 cm3 Kmol–1 at 2 K for 3–6, respectively. This reveals
revealed by structural analysis, the hexanuclear clusters of 1 the presence of dominant antiferromagnetic coupling in the
and 2 are constructed from two orthogonal linear trinuclear four compounds, which might be interpreted by the struc-
units through two O–C–C–O moieties that cannot transmit tural parameters, including the Cu···Cu separations and
magnetic interaction effectively [Equation (1)]. The CuII Cu–O–Cu angles, in the four compounds. The Cu···Cu dis-
center in the linear trinuclear unit interacts with the other tances in the dicubane cores are in the range of 3.1211(2)
two CuII ions through the Cu–N–N–Cu linkage with nearly to 3.1970(3) Å for 3, 3.1189(1) to 3.2056(3) Å for 4,
the same torsion angles, assuming they convey the same 3.0645(10) to 3.3289(9) Å for 5, and 3.0811(11) to
magnetic interactions (J). Thus, the magnetic data of 1 and 3.3418(10) Å for 6, which indicates that the cubanes in these
2 can be roughly estimated according to a simple model for compounds can be considered as a “6+0” type in the classi-
a centrosymmetric S = 1/2 linear trimer with the Hamilto- fication proposed by Tercero et al.[18] The structures and
nian H = –2J(S1S2 + S2S3),[17] in which S2 is the spin state magnetic couplings of this type of cubane have been seldom
of the central CuII ion, by employing a molecular field studied. Every adjacent two CuII ions in the dicubane cores
Eur. J. Inorg. Chem. 0000, 0–0
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FULL PAPER
of 3–6 are doubly bridged by alkoxido atoms with average The four chiral tridecanuclear clusters exhibit a rare hep-
Cu–O–Cu angles in the CuO2Cu units in the range of 95.4 tanuclear vertex-sharing dicubane core, and these clusters
to 98.9° for 3, 95.5 to 98.9° for 4, 94.4 to 99.8° for 5, and represent the first examples of chiral clusters bearing dicub-
95.2 to –100.4° for 6, which might favor antiferromagnetic ane cores. The results indicate that the introduction of a
interactions rather than ferromagnetic interactions between methoxyl group onto the ligand does not have much of an
the CuII ions, as supposed by similar cases.[11b–11d,19] An- influence on the skeletons of the thus-formed complexes,
other six CuII ions in 3–6 interact with the dicubane cores but it does reduce the symmetry of the skeleton. These re-
through Cu–N–N–Cu linkages with Cu···Cu separations of sults open promising perspectives towards the construction
4.7170(3)–4.8057(3) Å for 3, 4.7248(2)–4.8095(2) Å for 4, of more esthetic high-nuclear clusters from analogous li-
4.7507–4.7864 Å for 5, and 4.7792(14)–4.8027(15) Å for 6, gands by adjusting the reaction parameters. The magnetic
which are reported to mediate antiferromagnetic interac- measurements revealed the presence of overall antiferro-
tions between CuII ions.[20]
magnetic interactions between the metal ions in these com-
plexes.
Experimental Section
Materials and General Methods: The two pairs of chiral ligands
[(2R,3R)-BSH/(2S,3S)-BSH and (2R,3R)-MBSH/(2S,3S)-MBSH]
used in this study, as well as the materials used in their synthesis,
that is, (2R,3R)/(2S,3S)-2,3-dihydroxybutanedihydrazide, were pre-
pared following procedures described in the Supporting Infor-
mation. Other chemicals were used as obtained without further pu-
rification. Infrared spectra were recorded as KBr pellets by using
a Nicolet 360 FTIR spectrometer. Mass spectra were recorded with
a Bruker Esquire HCT spectrometer. Elemental analyses (C, H,
and N) were performed with a Vario EL analyzer. Powder X-ray
diffraction data were collected with a Rigaku D/max 2500v/pc dif-
fractometer with Cu-Kα radiation (λ = 1.5418 Å). Magnetic suscep-
tibilities were determined for crystalline samples at an applied mag-
netic field of 1000 Oe by using a Quantum Design MPMS-XL
SQUID magnetometer in the range from 300 to 2 K. Data were
corrected for the diamagnetic contribution calculated from Pascal
constants and the diamagnetism of the sample and sample holder
were taken into account. Circular dichroism spectra in the solid
state were recorded at room temperature with a JASCO J-810 CD
spectrometer as KBr pellets.
Figure 5. Plots of χm and χmT versus T for 3 and 4.
CAUTION! Perchlorate salts are potentially explosive. The experi-
ments were performed in an isolated room and experimenters were
equipped with safeguards. Only a small amount of the materials
should be prepared and handled with great care.
Synthesis of [Cu6{(2R,3R)-BSH}2(C5H5N)10]2[C5H6N]3(ClO4)7·
CH3OH·C5H5N (1): (2R,3R)-BSH (0.0390 g, 0.1 mmol) was dis-
solved in methanol (8 mL) at room temperature with stirring. Sub-
sequently,
a methanol solution (8 mL) of Cu(ClO4)2·6H2O
(0.1105 g, 0.3 mmol) was added dropwise. After stirring for another
3 h, pyridine (1 mL) was added. The resulting mixture was stirred
for another 5 h to give a green solution that was filtered. The fil-
trate was allowed to evaporate at ambient temperature for four
weeks to give dark green blocks of crystals of 1, yield 75%. IR
Figure 6. Plots of χm and χmT versus T for 5 and 6.
Conclusions
(KBr pellet): ν = 3438 (m), 1607 (s), 1547 (vs), 1484 (w), 1465 (w),
˜
1449 (m), 1377 (w), 1311 (w), 1220 (w), 1200 (w), 1152 (m), 1090
(br., s), 966 (w), 908 (w), 796 (w), 757 (m), 699 (m), 623 (m), 513 (w)
cm–1. C193H179Cl7Cu12N40O53 (4917.39): calcd. C 47.14, H 3.67, N
11.39; found C 47.28, H 3.40, N 11.67.
In summary, two enantiomeric pairs of ligands were de-
signed and prepared. Their reactions with cupric salts gave
one enantiomeric pair of chiral hexanuclear clusters and
two enantiomeric pairs of chiral tridecanuclear clusters. The
selection of appropriate bases is of importance for their for-
mation. The anions of the CuII salts contribute significantly
to the construction of different types of cluster skeletons.
The two hexanuclear clusters feature two nearly orthogonal
[Cu6{(2S,3S)-BSH}2(C5H5N)10]2[C5H6N]3(ClO4)7·CH3OH·C5H5N
(2): Prepared in a way similar to that of 1 by using (2S,3S)-BSH
instead of (2R,3R)-BSH, yield 78%. IR (KBr pellet): ν = 3439 (m),
˜
1608 (s), 1546 (vs), 1486 (w), 1465 (w), 1449 (m), 1376 (w), 1317
(w), 1219 (w), 1199 (w), 1151 (m), 1121 (s), 1109 (s), 966 (w), 908
linear trinuclear units that are cross-linked to each other. (w), 799 (w), 755 (m), 698 (m), 626 (m), 492 (w) cm– 1
.
Eur. J. Inorg. Chem. 0000, 0–0
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FULL PAPER
C193H179Cl7Cu12N40O53 (4917.39): calcd. C 47.14, H 3.67, N 11.39;
found C 47.39, H 3.88, N 11.56.
ring for 3 h, pyridine (1 mL) and a water solution (1 mL) of pyr-
azine (0.0100 g, 0.1 mmol) were added dropwise. The resulting mix-
ture was stirred for another 5 h to give a dark green clear solution
that was filtered. The filtrate was allowed to evaporate at ambient
temperature for two weeks to give dark green block crystals of 5,
[Cu13{(2R,3R)-BSH}3(OH)2(CH3COO)6(C5H5N)6(DMF)3]·
6DMF·3H2O (3): (2R,3R)-BSH (0.0390 g, 0.1 mmol) was dissolved
in DMF (5 mL) at room temperature with stirring. Subsequently,
a DMF solution (5 mL) of [Cu2(OAc)4(H2O)2] (0.0596 g,
0.15 mmol) was added. After stirring for another 3 h, pyridine
(1 mL) and a water solution (1 mL) of pyrazine (0.0100 g,
0.1 mmol) was added. The resulting mixture was stirred for another
5 h to give a dark green clear solution that was filtered. The filtrate
was allowed to evaporate at ambient temperature for three weeks
to give dark green block crystals of 3, yield 80%. IR (KBr pellet):
yield 70%. IR (KBr pellet): ν = 3414 (s), 1607 (s), 1540 (vs), 1467
˜
(w), 1439 (m), 1386 (m), 1315 (w), 1246 (m), 1218 (m), 1110 (m),
1087 (w), 1048 (w), 968 (w), 857 (w), 743 (m), 695 (w), 509 (w)
cm–1. C106H146Cu13N22O52 (3386.47): calcd. C 37.59, H 4.35, N
9.10; found C 37.28, H 4.60, N 8.88.
[Cu13{(2S,3S)-MBSH}3(OH)2(CH3COO)6(C5H5N)2(DMF)8]·6H2O
(6): Prepared in a way similar to that of 5 by using (2S,3S)-MBSH
ν = 3414 (br., m), 3048 (w), 2871 (w), 1662 (m), 1603 (s), 1537 (s),
˜
instead of (2R,3R)-MBSH, yield 75%. IR (KBr pellet): ν = 3358
˜
1487 (w), 1465 (w), 1448 (m), 1386 (m), 1330 (w), 1249 (w), 1221
(w), 1200 (m), 1149 (m), 1124 (w), 1095 (w), 1074 (w), 1045 (w),
1018 (w), 908 (w), 800 (w), 757 (m), 697 (m), 671 (w), 594 (w), 497
(w) cm–1. C123H155Cu13N27O44 (3541.76): calcd. C 41.71, H 4.41,
N 10.68; found C 41.40, H 4.58, N 10.90.
(br., s), 1604 (s), 1588 (s), 1546 (vs), 1467 (m), 1434 (m), 1388 (m),
1309 (w), 1246 (m), 1216 (m), 1106 (m), 1083 (w), 964 (w), 855 (w),
747 (m), 626 (m), 596 (w) cm–1. C106H146Cu13N22O52 (3386.47):
calcd. C 37.59, H 4.35, N 9.10; found C 37.78, H 4.28, N 9.02.
X-ray Crystallography: The X-ray diffraction data of 1–6 were col-
lected with a Bruker Smart Apex-II CCD diffractometer by using
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). Ab-
sorption correction were applied by using the multiscan program
SADABS.[21] The structures were solved by direct methods by using
SHELXS-97[22] and were refined by using the SHELXL-97 pro-
gram[23] or the corresponding programs in the SHELXTL pack-
age.[24] Full-matrix least-squares refinements on F2 by using all data
were performed with anisotropic displacement parameters applied
to all non-hydrogen atoms. H atoms attached to C atoms were in-
[Cu13{(2S,3S)-BSH}3(OH)2(CH3COO)6(C5H5N)6(DMF)3]·
6DMF·3H2O (4): Prepared in a way similar to that of 3 by using
(2S,3S)-BSH instead of (2R,3R)-BSH, yield 78%. IR (KBr pellet):
ν = 3418 (br., m), 3048 (w), 2871 (w), 1663 (m), 1605 (s), 1532 (s),
˜
1487 (w), 1466 (w), 1444 (m), 1386 (m), 1327 (w), 1249 (w), 1220
(w), 1200 (m), 1149 (m), 1124 (w), 1095 (w), 1073 (w), 1045 (w),
1018 (w), 908 (w), 800 (w), 756 (m), 698 (m), 670 (w), 592 (w), 498
(w) cm–1. C123H155Cu13N27O44 (3541.76): calcd. C 41.71, H 4.41,
N 10.68; found C 41.49, H 4.29, N 10.39.
[Cu13{(2R,3R)-MBSH}3(OH)2(CH3COO)6(C5H5N)2(DMF)8]· cluded in geometrically calculated positions for all structures by
6H2O (5): A DMF solution (5 mL) of [Cu2(OAc)4(H2O)2] using a riding model and were refined isotropically. H atoms on N
(0.0596 g, 0.15 mmol) was added dropwise to a stirred mixture of
(2R,3R)-MBSH (0.039 g, 0.1 mmol) and DMF (5 mL). After stir-
and O atoms were placed in calculated positions. Figures were cre-
ated with the OLEX program.[25] In 1 and 2, one ClO4– anion, two
Table 1. Crystallographic data for compounds 1–6.
1
2
3
4
5
6
Formula
Mr [gmol–1]
T [K]
C
193H179Cl7Cu12N40O53 C193H179Cl7Cu12N40O53 C123H155Cu13N27O44 C123H155Cu13N27O44 C106H146Cu13N22O52 C106H146Cu13N22O52
4917.39
298(2)
4917.39
298(2)
3541.76
296(2)
3541.76
296(2)
3386.47
296(2)
3386.47
296(2)
λ [Å]
0.71073
orthorhombic
P21212
17.8627(18)
24.089(3)
24.676(3)
90
0.71073
orthorhombic
P21212
17.8876(19)
24.194(3)
24.719(3)
90
0.71073
trigonal
R3
25.8714(18)
25.8714(18)
19.639(3)
90
0.71073
trigonal
R3
25.9123(14)
25.9123(14)
19.427(2)
90
0.71073
orthorhombic
C2221
17.302(6)
26.280(10)
31.411(11)
90
0.71073
orthorhombic
C2221
17.281(7)
26.362(11)
31.331(13)
90
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
90
90
90
90
90
90
γ [°]
90
10618(2)
2
1.538
1.351
90
10698(2)
2
1.527
1.341
120
11383.6(19)
3
1.550
1.866
120
11296.5(15)
3
1.562
1.881
90
14283(9)
4
1.575
1.982
90
V [Å3]
14274(10)
4
1.576
1.983
6916
Z
ρcalcd. [gcm–3]
μ [mm–1]
F(000)
5016
5016
5433
5433
6916
Crystal size
[mm]
0.38ϫ0.30ϫ0.20
0.40ϫ0.28ϫ0.25
0.48ϫ0.42ϫ0.38
0.48ϫ0.42ϫ0.38
0.45ϫ0.28ϫ0.25
0.43ϫ0.35ϫ0.25
θ range [°]
Reflns. collected 49336
1.18 to 25.02
1.18 to 25.02
54796
2.62 to 25.02
26892
2.62 to 25.01
20640
2.40 to 25.01
43813
2.36 to 25.02
48714
Data/parameters 18696/1438
18859/1434
0.0630
1.051
0.0571
0.1256
8657/598
0.0528
1.045
0.0482
0.1129
8568/628
0.0317
1.017
0.0574
0.1377
12123/638
0.1519
1.190
0.1550
0.3567
12391/745
0.0974
1.021
0.0619
0.1457
Rint
0.0748
1.032
GOF on F2
R1 [IϾ2σ(I)]
wR2 [IϾ2σ(I)]
R1 (all data)
wR2 (all data)
0.0555
0.1177
0.1080
0.1253
0.0999
0.1339
0.0737
0.1315
0.0763
0.1523
0.2165
0.4078
0.0948
0.1699
Flack parameter –0.033(13)
–0.011(13)
–0.007(18)
0.02(2)
0.10(6)
–0.01(2)
Eur. J. Inorg. Chem. 0000, 0–0
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FULL PAPER
C6H5NH+ cations, and one methanol molecule were refined in a
disordered manner. One water molecule in 3 and 4 was disordered
over two positions. The two HO– ions (O12 and O13) in 3 and 4
were located at the special sites with occupancies of 0.3333. Some
geometric restraints (DFIX, FLAT, SADI, or SIMU) were used in
modeling the poor geometries of one coordinated pyridine mol-
ecule and one coordinated CH3COO– ion in 3 and 4. Some geomet-
ric restraints were also used in modeling the poor geometries of
some coordinated DMF molecules and CH3COO– ions in 5. Of
12123 intensity reflections used in the refinement of 5, only 6796
reflections were considered “observed”; consequently, about 44%
of the data represent weak reflections, which led to R and wR val-
ues that were higher for 5 than for the other compounds. However,
the model for the structure of 5 was determined without any doubt.
Crystallographic data of 1–6 are given in Table 1. Selected bond
lengths and angles for 1–6 are listed in Tables S1–S6.
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[8]
Acknowledgments
The authors thank for the financial support by the National Natu-
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20971029, and 21261004), the Program for New Century Excellent
Talents in University (NCET-10-0095), and the Guangxi Natural
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Received: August 17, 2014
Published Online: ᭿
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Chiral Magnetic Cu Clusters
Z. Chen, S. Zhou, Y. Shen, H. Zou,
D. Liu, F. Liang* ............................ 1–11
Six chiral clusters of two pairs of 2,3-di-
hydroxybutanedioyl dihydrazones, four of
which represent the first examples of chiral
clusters bearing dicubane cores, are pre-
sented. All six compounds are enantiomers
of each other. Magnetic studies reveal the
presence of overall antiferromagnetic inter-
actions in these compounds.
Copper(II) Clusters of Two Pairs of 2,3-Di-
hydroxybutanedioyl Dihydrazones: Syn-
thesis, Structure, and Magnetic Properties
Keywords: Cluster compounds / Copper /
Magnetic properties / Chirality / Structure
elucidation
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