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Synthesis, structure and properties of {M4 O4 } cubanes containing nickel(II)

and cobalt(II)†‡
Katharina Isele,a Fabienne Gigon,a Alan F. Williams,*a Gérald Bernardinelli,b Patrick Franzc and
Silvio Decurtinsc
Received 4th October 2006, Accepted 6th November 2006
First published as an Advance Article on the web 21st November 2006
DOI: 10.1039/b614424a

A survey of the crystal structures containing simple {M4 O4 } cubane units is reported. It shows that the
Published on 21 November 2006 on http://pubs.rsc.org | doi:10.1039/B614424A

average M–M distance in these complexes is relatively constant for a given metal ion M. The structures
are all distorted from the idealised cube to a T d structure, and most show a further distortion which,
however, usually maintains some elements of symmetry. A system for classifying the different types of
ligand in these complexes is proposed. Two new cubanes of cobalt(II) and nickel(II) with the ligand
(R,R)-bis-1,2-(1-methylbenzimidazol-2-yl)ethane-1,2-diol, (R,R)-1 or its enantiomer have been isolated
and the crystal structure of the cobalt(II) complex confirms the cubane structure. Electronic, CD and
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1
H NMR spectra and magnetic susceptibility data are reported. The magnetic data for these and other
compounds in the literature are discussed in terms of the structural parameters.

Introduction
Coordination chemistry is increasingly interested by the study
of polynuclear complexes and the novel properties associated
with the interactions of two or more metal centres.1 Interest has
been focussed on complexes where magnetic exchange is observed
between paramagnetic metal ions, both from a theoretical point of
Scheme 1
view, and also with the aim of developing single molecule magnets.2
We have been interested in the design of ligands which favour the
formation of polynuclear species and which may potentially con- The cubanes, which we shall define in this paper as complexes
trol the structure. The ligand (R,R)-bis-1,2(1-methylbenzimidazol- with a M4 X4 core in which the metal ions occupy four non-
2-yl)ethane-1,2-diol, (R,R)-1 (Scheme 1) possesses potentially neighbouring vertices of a cube, and the triply bridging X units
bridging alcohol functions which may be deprotonated to give the four others (Scheme 2), are a particularly interesting family.
alkoxo-functions which are good bridging ligands, and offer a The Fe4 S4 cubanes are well known in biology as electron transfer
pathway for magnetic exchange.3 We will denote the deprotonated agents.5,6 Very recently, a heteronuclear Mn3 CaO4 cubane was
forms as 1 − H or 1 − 2H. The ligand and its enantiomer (S,S)- shown to be present at the active site of the oxygen evolving
1 are readily prepared in enantiomerically pure form from the centre of photosystem II,7 and a Fe3 MoS4 cubane has been
appropriate isomer of tartaric acid. identified at the active site of nitrogenase.8 M4 O4 units show
We have previously reported on the chemistry of this ligand interesting magnetic exchange properties and may under certain
in simple mononuclear complexes [M(1)2 ]n+ 4 and more recently circumstances act as single molecule magnets.9–13
on the various polynuclear complexes formed with copper(II).3
In this paper we show that ligand 1 forms cubane complexes
with cobalt(II) and nickel(II) and report on the properties of these
complexes.

a
Department of Inorganic chemistry, University of Geneva, 30 quai Scheme 2
Ernest-Ansermet, CH-1211, Geneva, Switzerland. E-mail: Alan.Williams@
chiam.unige.ch
b
Laboratory of X-ray Crystallography, University of Geneva, 4 quai Ernest- Although many such cubane complexes are now known, there
Ansermet, CH-1211, Geneva 4, Switzerland has been little comparative discussion of the structures. We
c
Department of Chemistry and Biochemistry, Universität Bern, Freiestrasse therefore review briefly the structures in the Cambridge Structural
3, CH-3009, Berne, Switzerland Database for cobalt and nickel, and propose a simple structural
† Dedicated to Professor Hans Güdel on the occasion of his retirement.
classification which may be used for correlation with the properties
‡ Electronic supplementary information (ESI) available: IR spectra of
[Co4 ((R,R)-1 − H)4 ](ClO4 )4 (C2 H6 OH)9 and [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 - of the complexes. To simplify discussion of our results, we begin
(H2 O)5 . See DOI: 10.1039/b614424a with this survey.

332 | Dalton Trans., 2007, 332–341 This journal is © The Royal Society of Chemistry 2007
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Results cobalt(III). This constancy of the average M–M distance may be

interpreted in terms of a well-defined M4 O4 unit which may be
Structural analysis of cubanes distorted slightly but which is not greatly affected by the external
ligands.
The term cubane has been used to describe many complexes which
show great structural variety. In this section we discuss the features Distortion modes. The M–M distances afford a simple method
which allow one to distinguish and classify the structures. of analysing the distortion of the M4 tetrahedron (Scheme 3). If the
tetrahedron is distorted by extension along a S4 axis, four M–M
Metric properties. An ideal cubane has twelve equal bond
distances will be increased, and two others will remain the same.
lengths and twenty-four bond angles of 90◦ . Such ideality is
Distortion along a C 3 axis will give two sets of three equal M–
not encountered in practice, notably because three bonds at
M distances, whereas a distortion which maintains three C 2 axes
90◦ are rarely observed at the bridging oxygen atom. An sp3
will give three pairs of M–M distances. The D2 symmetry may
hybridised oxygen atom would have three angles of 109.5◦ , and
be further distorted to a C 2 system. This very simple approach
this may be achieved by compressing the four oxygens along the
Published on 21 November 2006 on http://pubs.rsc.org | doi:10.1039/B614424A

accounts for the majority of the compounds in the database: out

body diagonals of the cube, increasing the angles at oxygen, but
of 69 compounds, 40 show a S4 distortion, 14 a D2 or C 2 distortion
concurrently decreasing the angles at the metal below 90◦ . We may
and 5 a C 3 distortion, the remaining 10 adopting lower symmetry.
measure the magnitude of this effect by the average M–O–M bond
The magnitude of the distortion may be estimated roughly from
angle or by calculating the sum of the angles at an oxygen vertex,
the standard deviation of the six M–M distances: we have taken
the value for an ideal cubane being 270◦ and that for a sp3 oxygen
values below 0.03 Å to correspond to a low distortion, and those
328.5◦ . As a consequence of this distortion, the M4 O4 units may
greater than 0.1 Å as highly distorted. Table 2 shows mean M–M
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be regarded as interpenetrating M4 and O4 tetrahedra, the whole

distances for the 20 cobalt(II) cubanes in the CSD, and, for a given
possessing T d symmetry. We will refer to this distortion of the ideal
compound, the standard deviation of the M–M distance, and the
cube as the tetrahedral distortion.
deviation of each M–M distance from the mean, which allows
We have searched the Cambridge Structural Database (version
the ready identification of the distortion mode. We have taken
5.27 with updates of January 2006) for structures containing
extensions as shown in Scheme 3 to be positive; a negative S4
the M4 O4 unit where M = Co or Ni, excluding structures with
distortion corresponds to a compression and will give four bonds
errors. We also excluded more complicated structures such as
shorter than average and two longer.
face-sharing cubanes where it appeared that the geometry of
the M4 O4 unit was likely to be perturbed by the oligomerisation.
This left a total of 70 structures, 40 with Ni(II), 20 with Co(II), one
mixed valence structure with two Co(II) and two Co(III), and 9 with
Co(III). A summary of the most important parameters is given in
Table 1. In all cases the tetrahedral distortion discussed above is
observed: the average M–O–M angles are greater than 90◦ , and
the O–M–O angles less than 90◦ . Although the individual angles
vary by several degrees, the sum of the angles at a given oxygen
vertex shows a much smaller variation.
The tetrahedron of metal ions may be characterised by the
six M–M distances which will be equal in an ideal tetrahedral
structure. If we examine these distances we observe that the
individual values vary by up to 0.3 Å within a given structure
(i.e., by about 10%), but from one structure to another the mean
Scheme 3 The M4 tetrahedron of the cubane (shown with dashed lines,
value is remarkably constant for a given metal ion, with a standard top) may be distorted in three ways while retaining some element of
deviation of the order of 0.03 Å. The average values for cobalt(II) tetrahedral symmetry. For the D2 distortion only one C 2 axis is shown.
and nickel(II) are similar but that for cobalt(III) is much smaller.
This is of course a consequence of the shorter M–O bond distances For example, the structure UMAHAR14 shows four bonds
expected for cobalt(III). The average M–M distances for the mixed longer than the average and two which are shorter, corresponding
valence cobalt cubane lie in between the values for cobalt(II) and to an elongation along the S4 axis or positive distortion, while

Table 1 Average structural parameters for cobalt and nickel cubanes

Co(II) Co(III) Ni(II)

Number of compounds 20 9 40
Mean M–M distance/Å 3.14(3) 2.80(3) 3.11(3)
Maximum and minimum M–M distances/Å 3.368, 2.854 3.060, 2.641 3.269, 2.824
Mean M–O distance/Å 2.094(15) 1.885(12) 2.064(11)
Mean M–O–M angle/◦ 97.2(7) 95.9(6) 97.6(6)
Mean pyramidal angle/◦ 291.8 287.8 292.9
Mean O–O distance/Å 2.747(17) 2.510(11) 2.698(18)
Mean O–O/M–M ratio 0.875 0.898 0.869

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Table 2 Data for cobalt(II) cubanes in the CSD. Distortion: magnitude of the distortion based on the s.d. of the mean Co–Co distance (low < 0.03 Å;
high > 0.1 Å). Symmetry: approximate symmetry of the distortion from T d . Dn : the difference between the nth Co–Co distance of the cubane and the
mean value. Tet. Parm: ratio of the average O–O distance to the average M–M distance. Ligand coding as described in the text

Co–Co Distortion, Tet.

CSD code mean/Å s.d./Å symmetry D1 /Å D2 /Å D3 /Å D4 /Å D5 /Å D6 /Å Parm. Ligand coding Ref.

TAWJEG 3.143 0.035 Medium −0.015 0.029 −0.052 −0.012 0.002 0.048 0.871 Co4 /0s4 /m10 b 24
UMAHAR 3.103 0.144 High, S4 + −0.153 0.097 0.084 0.091 0.097 −0.215 0.886 Co4 /0s4 /m4 b2 d2 14
XEZMUK 3.133 0.088 Medium, C 3 − 0.081 0.081 −0.080 0.081 −0.080 −0.080 0.879 Co4 /0s4 /m6 b3 16
XOVNAX 3.118 0.005 Low, C 3 + 0.005 0.004 0.004 −0.005 −0.005 −0.005 0.883 Co4 /0s4 /m6 b3 25
ACABEL 3.134 0.042 Medium, S4 − −0.013 −0.030 0.033 0.069 −0.031 −0.030 0.885 Co4 /0s4 /m4 b4 26
BEWDUC 3.128 0.110 High, C 2 0.018 −0.095 0.201 −0.044 −0.095 0.018 0.883 Co4 /0s4 /m4 b4 27
CEVSEB 3.109 0.046 Medium, S4 − −0.030 0.059 −0.030 −0.030 0.059 −0.030 0.884 Co4 /0s4 /m4 b4 28
MAKFAG 3.132 0.046 Medium, S4 − −0.031 0.052 −0.023 −0.037 0.065 −0.028 0.879 Co4 /0s4 /m4 b4 21
OBOYOT 3.101 0.025 Low, D2 −0.011 0.027 −0.020 −0.020 0.036 −0.011 0.876 Co4 /0s4 /m4 b4 29
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XOVNEB 3.118 0.021 Low, S4 − 0.027 −0.014 −0.014 −0.014 −0.014 0.027 0.881 Co4 /0s4 /m4 b4 25
HAJCIF 3.099 0.147 High, S4 + −0.139 0.088 0.099 0.095 0.089 −0.234 0.888 Co4 /0s4 /m4 d2 b2 30
HAJFAA 3.099 0.126 High, S4 + 0.090 0.078 −0.169 −0.155 0.083 0.073 0.892 Co4 /0s4 /m4 d2 b2 30
IWOKOU 3.147 0.105 High, D2 −0.144 0.039 0.094 0.095 0.036 −0.119 0.864 Co4 /0s4 /d2 b4 17
RAPXIQ 3.062 0.140 High, S4 + −0.150 0.089 0.083 0.095 0.092 −0.208 0.886 Co4 /0s4 /m4 d2 b2 31
LILTUV 3.147 0.119 High, D2 −0.136 0.131 0.007 0.007 0.129 −0.136 0.860 Co4 /0s4 /d332 23
FUXNOB 3.165 0.053 Medium −0.043 −0.019 −0.026 −0.017 0.002 0.103 0.874 Co4 /1s4 /m6 32
UMUFOX 3.188 0.133 High, S4 − 0.180 −0.098 −0.085 −0.094 −0.066 0.163 0.880 Co4 /1s4 /d4 15
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JAXTOR 3.241 0.012 Low 0.002 0.011 0.002 −0.015 −0.013 0.016 0.848 Co4 /2s4 /m4 22
MAWZOZ 3.242 0.029 Low, C 2 −0.034 0.037 −0.022 −0.013 0.030 0.004 0.842 Co4 /2s4 /m4 20
ILUHUS 3.173 0.036 Medium, C 2 0.014 −0.013 0.043 0.034 −0.032 −0.046 0.861 Co4 /3s4 / 13
[Co4 (1 − H)4 ]4+ 3.229 0.121 High, C 2 0.042 −0.059 0.128 0.128 −0.059 −0.179 0.864 Co4 /2s212 3s2 /

UMUFOX15 has two extended and four shortened bonds, corre- more significant change is when the bridging oxygen atoms are
sponding to a flattening of the tetrahedron or negative distortion. part of alkoxo- or phenoxo-units which are linked to one or more
XEZMUK16 with three bonds shortened and three lengthened has terminal ligands. We will refer to this arrangement as a supported
a negative C 3 distortion, and IWOKOU17 a D2 structure with three bridging ligand, using a term which has previously been used in
different pairs of roughly equal distances. Tables for cobalt(III) and the chemistry of polynuclear copper compounds.3 In this case the
nickel(II) compounds are given in the supplementary material. The different binding sites may be prearranged to favour the formation
S4 distortion has been mentioned previously in studies18 of iron- of the cubane structure, although to our knowledge there are
sulfur protein models where it is often observed18,19 (note that these currently no thermodynamic data which allow one to judge how
authors refer to it as a D2d distortion). great a stabilisation of the polynuclear species is achieved.
The bridging oxygen may be linked to one, two, or three
Oxygen–oxygen distances. Now we may examine the O4 tetra-
metal ions, and we will call these mono-, di- or ter-supported
hedron. The tetrahedral distortion of the cube brings the oxygen
(Scheme 4). An example of a monosupported ligand is 2-
atoms closer to one another, and one may ask to what extent O–
methylquinolin-8-olate (UMUFOX15 ), of a disupported ligand
O repulsion is important. For Ni(II) and Co(II) the average O–O
bis(2-pyridyl)hydroxymethanolate (MAWZOZ20 ), and of a tersup-
distances are similar and close to 2.7 Å, but are slightly smaller for
ported ligand citrate (ILUHUS13 ).
cobalt(III) at 2.51 Å. These values are smaller than twice the van
der Waals radius of oxygen (1.40 Å) and comparable to the values
commonly used for the ionic radius of oxygen. We may therefore
deduce that some O–O interaction is present. The ratio of the
mean O–O distance to the mean M–M distance may be taken as a
measure of the tetrahedral distortion: a value of 1 is expected for
a perfect cube. The values vary only by a few percent for a given
group of compounds (see Table 2 for the cobalt(II) complexes), but
Scheme 4 Classification of bridging ligands.
are significantly greater for the cobalt(III) complexes.
If a mixed valence MII 2 MIII 2 O4 system is considered, we may
One quickly becomes aware of the difficulty of comparing struc-
easily predict that the intermetal distances will follow the or-
tures with different ligands. Often the connectivity only becomes
der MIII –MIII < MIII –MII < MII –MII leading to a C 2 system which
clear after rotating a computer-generated image so as to examine
is indeed observed. For MII MIII 3 O4 and MII 3 MIII O4 one would
the complex from different angles. We suggest here a relatively
predict negative and positive C 3 distorted structures respectively.
simple nomenclature for coding the different types of ligands in
Ligand description. For an octahedral metal ion, the simplest these structures. Any given structure may be regarded as composed
cubane will have the composition [L3 M(OR)]4 where OR is the of four metals and four bridging atoms (in our case oxygen) which
l3 -bridging ligand, and L is a monodentate terminal ligand which form the vertices of the cube. The coordination sphere of the
completes the octahedral coordination of the metal. This structure metal is then completed by a certain number of terminal ligands.
may be modified in several ways. A trivial change is to replace the We denote the terminal ligands as m (monodentate), b (bidentate)
monodentate terminal ligands by bidentate or tridentate ones. A or t (tridentate). The bridging atoms may be unsupported (0s) or

334 | Dalton Trans., 2007, 332–341 This journal is © The Royal Society of Chemistry 2007

supported (1s, 2s, or 3s, the number designating the number
of arms linking the bridging atom to a terminal ligand). We
then code the complex as a whole by metal4 /bridging ligand4 /
terminal ligandsn . Thus the simplest cubane [L3 M(OR)]4 is M4 /
0s4 /m12 , involving four unsupported (0s) OR groups and twelve
terminal monodentate ligands m. Substitution of two terminal
monodentate ligands on each metal by a bidentate ligand gives
M4 /0s4 /m4 b4 . This is a common motif as in MAKFAG21
[Co(OMe)(dpm)(MeOH)]4 which has bridging methoxides (0s)
and the terminal ligands of each metal are an dipivaloylmethane
(dpm, type b) and a methanol (m). When supported ligands are
present, they occupy some of the terminal sites. For example
JAXTOR22 contains a di-supported bis(2-pyridyl)hydroxy-
Published on 21 November 2006 on http://pubs.rsc.org | doi:10.1039/B614424A
methanolate 2s ligand where the two pyridine nitrogens occupy
two of the terminal sites, the third being occupied by a
monodentate acetate to give Co4 /2s4 /m4 .
There are two subtleties which need to be taken into account.
There is sometimes a terminal ligand which binds to more than
one metal. For example, carboxylates are often found to bridge
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two metals across a face diagonal of the cube. We denote these
as d (diagonal) as in UMUFOX,15 Co4 /1s4 /d4 where the 2-
methylquinolin-8-olate ligand is monosupported, the quinoline
nitrogen occupying one of the terminal sites while the two
remaining terminal sites are occupied by diagonally bridging
pivalates. A further complication arises when the bridging or
diagonal ligand binds to a metal by more than one functionality.
This may be indicated by adding the number of binding groups as
in LILTUV23 (Scheme 5) where three functions bind to each metal.
In the absence of a qualifier, the ligand is assumed to bind by one
atom to each metal only (i.e., d is equivalent to d11, 3s to 3s111).
Scheme 5
Crystal structure of [Co4 ((R,R)-1 − H)4 ](ClO4 )4 ·9EtOH
Rose coloured crystals suitable for X-ray diffraction were obtained
by slow diffusion of ethanol into a solution of ligand (R,R)-1,
cobalt(II) perchlorate, and base. The crystal structure shows the
presence of the tetranuclear complex [Co4 ((R,R)-1 − H)4 ]4+ de-
duced from ESMS (Fig. 1) which lies on the twofold axis (parallel
to a) of the orthorhombic space group C2221 . The complex has the
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Co4 O4 cubane structure with four deprotonated alcohol functions
of ligand (R,R)-1 supplying the bridging oxygens. Each cobalt
is further coordinated by two benzimidazole functions and an
alcohol function from each ligand. The two crystallographically
distinct ligands show different coordination modes. Both possess
a triply bridging alkoxide function, but ligand a binds one metal
through a benzimidazole and an alcohol, and a second through a
benzimidazole; ligand b binds all three metal ions bridged by the
alkoxide using a benzimidazole, an alcohol and a benzimidazole
respectively. Using the nomenclature developed above, ligand a
may be described as 2s21, and ligand b as 3s, giving a complete
structural description as Co4 /2s212 3s2 /.
Fig. 1 Partial structure of the [Co4 ((R,R)-1 − H)4 ]4+ cation showing the
two independent ligands and the Co4 O4 core. The twofold axis generates
the primed atoms.
Both ligands adopt a conformation in which the benzimidazoles
are mutually trans. Consequently the diol functions are mutually
gauche: the diol dihedral angle (measured as O1–C9–C10–O2) is
47.1(7)◦ for ligand a and 49.0(7)◦ for ligand b, smaller than the
60◦ expected for a gauche conformation. The coordination modes
shown by ligand 1 in this complex are quite different from the seven
previously recorded for this ligand. In particular they are different
from that observed for the tetranuclear copper cubane with the
non-methylated ligand, where the unprotonated alcohol function
does not coordinate.3 We may also note that the conformation is
in agreement with the steric effects observed for the methyl group
bound to the benzimidazole nitrogen.33 The terminal cobalt–
oxygen and cobalt–nitrogen bond distances are normal. The
average Co–Co distance (3.229 Å) is slightly greater than the mean
in Table 1, and the degree of distortion (as indicated by the variance
of the Co–Co distances) is high. The general features of the Co4 O4
core, however, do not show significant differences from those in
the literature. There are two intramolecular stacking interactions
between benzimidazoles related by a twofold axis, with interplane
angles of 0.5(2) and 13.6(2)◦ for ligands a and b respectively.
The cations pack in layers in the ab plane (Fig. 2) and the
layers are separated by perchlorate ions and ethanol molecules.
Hydrogen bonds are observed between the alcohol functions of
the ligand and ethanol solvate molecules which are themselves
hydrogen bonded to perchlorate ions. Five ethanol molecules (one
of which is disordered about a twofold axis) form a pentagonal
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Fig. 2 View of one of the cation layers in the crystallographic ab plane.

motif linked by hydrogen bonds in a R55 arrangement.34,35 The

solvate molecules are readily lost and the crystals are thus rather
unstable.
It proved impossible to obtain crystals of the nickel complex
suitable for accurate X-ray diffraction studies. The best crystals
obtained allowed us only to obtain an estimate of the unit cell
as orthorhombic P (a = 13.534(4), b = 24.05(2), c = 30.03(1) Å)
with a volume of 9772.4 Å3 , slightly less than that for the cobalt
compound discussed above. This is at least consistent with the
existence of a tetranuclear complex, and on the basis of the ESMS
results and the similarity of the IR spectra of the two solids (Fig.
S1, ESI‡), we assume that the nickel complex is also a cubane.
Solvent loss was also observed with these crystals.
Electronic and circular dichroism spectra
The spectra obtained in solution and those obtained from diffuse
reflectance show maxima at the same wavelengths and support
the hypothesis that there is no structural change upon dissolution.
The d–d bands (Table 3, Fig. 3) are consistent with an octahedral
Fig. 3 Visible (a) and CD (b) spectra of [Co4 ((R,R)-1 − H)4 ]4+ in
acetonitrile solution.
geometry for the metal, and are slightly blue shifted with respect
to the aqua-ions, and red shifted with respect to the complexes
[M(1)2 ]2+ ,4 as would be expected for a MN2 O4 chromophore. The
CD spectra are normal for cobalt(II) and nickel(II) complexes.
Magnetic susceptibility
The magnetic susceptibility of cubane complexes has been studied
extensively in recent years. Their high nuclearity and the magnetic
exchange pathways offered by the triply bridging oxygen atoms
make them particularly interesting, and several complexes have
shown potential as single molecule magnets.9–13 The susceptibilities
of these complexes fall into three classes which are sketched below
(Fig. 4). Type A is generally the most common and shows a rise
in vT at low temperatures, until a sharp drop is observed below

Table 3 d–d Transitions (kmax /nm, e/dm3 mol−1 cm−1 ) and circular dichroism (kmax /nm, De/dm3 mol−1 cm−1 ) of [Ni4 ((S,S)-1 − H)4 ]4+ and [Co4 ((R,R)-1 −
H)4 ]4+ recorded in acetonitrile solution, and reflectivity data obtained in a MgO matrix

d–d Transitions
Absorption (kmax (e)) Reflectivity (kmin ) Assignment CD (kmax (De))

[Ni4 ((S,S)-1 − H)4 ]4+

3
1135 (10) 1155 T2g –3 A2g (m1 )
1
763 (sh) (7) 763 (sh) Eg –3 A2g 746 (−0.166)
3
662 (13) 660 T1g –3 A2g (m2 ) 663 (−0.204)
3
402 (31) 399 T1g (P)–3 A2g (m3 ) 414 (−0.236)

[Co4 ((R,R)-1 − H)4 ]4+

4
1044 (8) 1054 T2g –4 T1g (m1 )
4
704 (9) 682 A2g –4 T1g (m2 ) 702 (−0.153)
560 (76) 542 553 (−0.138)
4
527 (sh) (62) 480 (sh) T1g (P)–4 T1g (m3 ) 515 (0.372)
460 (50) 480 (sh) (0.118)
450 (−0.123)

336 | Dalton Trans., 2007, 332–341 This journal is © The Royal Society of Chemistry 2007

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Fig. 4 Schematic representation of the three types of magnetic behaviour
observed in these systems.
10 K. Type B shows a steady drop in vT starting in the range 50–
100 K and tending towards zero at very low temperatures. Both
types A and B have been observed for cobalt(II) and nickel(II) but
type C has only been seen with cobalt(II) compounds. vT falls
slightly with temperature showing rather irregular behaviour, and
is still quite high even at 2 K.
We have measured the magnetic susceptibility of [Ni4 ((S,S)-
1 − H)4 ](ClO4 )4 (H2 O)5 and [Co4 ((R,R)-1 − H)4 ](ClO4 )4 (C2 H5 OH)-
(H2 O)5 in the temperature range of 2 to 300 K. Fig. 5 and 6 show
the vT values plotted against temperature.
Fig. 5 Variable-temperature (300–2 K) magnetic susceptibility data
of compound [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 (H2 O)5 . The plot shows vT
against T.
The vT value of [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 (H2 O)5 at 300 K
is 5.32 emu K mol−1 and decreases to 0.25 emu K mol−1 at 2 K,
typical for a type B system. The room-temperature value is slightly
greater than the spin-only value of 4.0 emu K mol−1 for an S =
1 system with g = 2. The shape of the curve indicates an overall
antiferromagnetic exchange interaction between the nickel(II) ions.
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Fig. 6 Variable-temperature (300–2 K) magnetic susceptibility data of
compound [Co4 ((R,R)-1 − H)4 (CIO4 )4 (C2 H5 OH)(H2 O)5 . The plot shows
vT against T.
If we assume [Ni4 ((S,S)-1 − H)4 ]4+ to possess an ideal T d cubane
structure one may use an isotropic Heisenberg Hamiltonian (H =
−2J(S1 S2 + S1 S3 + S1 S4 + S2 S3 + S2 S4 + S3 S4 ). A least-squares
fit of this model to the data gave g = 2.35 and J = −3.57 cm−1
in agreement with an antiferromagnetic interaction between the
nickel(II) ions. However, as we discuss below, this is not a good
model for this system.
The susceptibility of [Co4 ((R,R)-1 − H)4 ](ClO4 )4 (C2 H5 OH)-
(H2 O)5 shows typical type C behaviour. The value of vT at
300 K is 11.2 emu K mol−1 greater than the spin-only value
of 7.5 (S = 3/2, g = 2), but typical for cobalt(II) cubanes, and
arises certainly from unquenched orbital angular momentum in
the pseudo-octahedral symmetry. The value of vT decreases with
temperature, but much less than a type B system, and shows a
small peak at 11 K. This peak was observed in the two other type
C systems in the literature,13,36 and is thus unlikely to be an artefact.
After this peak, vT continues to fall, but is still 9.7 emu K mol−1
at 1.8 K, well above the spin-only value.
It would be desirable to establish a correlation between the
crystal structures and the magnetic properties of these compounds,
and in particular the observation of ferro- or antiferromagnetism.
The magnetic exchange pathway is through the two alkoxo-ligands
which bridge each pair of metals in the cubane. It is generally
accepted that the value of the M–O–M bond angle is critical in
characterising the exchange and for nickel there is a consensus that
below 98–99◦ , the interaction will have ferromagnetic character,
and above this angle it will be antiferromagnetic.38,48 If we return
to our structural discussion above, it will be noted that the
average M–O–M angle in these structures is around 97◦ . This is
just on the ferromagnetic side of the boundary value, and indeed
ferromagnetic (type A) behaviour is observed more often that
others. It is equally clear, however, that a distortion will change
these angles by several degrees, and this would be expected to affect
the exchange pathways. If we consider the S4 distortion which is
the most common, then, if we assume that the bridging oxygen
remains in the centre of the triangular face, an S4 + distortion will
increase eight of the M–O–M angles, and decrease four; an S4 -
distortion will decrease eight and increase four. On the basis of
this reasoning we might expect that the S4 -distortion will favour
type A behaviour, whereas S4 + will favour type B. This is indeed
generally the case for the nickel systems for which structure and
Dalton Trans., 2007, 332–341 | 337
 View Online

Table 4 Comparison of magnetic and structural properties

M–O–M angles/◦

Compound Ligation mode Distortion Magnitude/Å Mean Max. Min. Magnetism Ref.

Nickel complexes
ELELIQ 0s4 /t4 Irreg. 0.067 97.2 101.3 96.1 A 37
EZIGAV 2s4 /m4 S4 + 0.005 97.4 97.5 97.2 A 11
ZAXJUD 0s4 /b4 m4 S4 − 0.036 97.6 100.2 96.0 A 38
AKISOCa 1s4 /m8 S4 − 0.033 98.3 100.5 97.4 A 9
AKISUI 1s4 /m8 S4 − 0.032 98.2 99.6 97.5 A 9
BEPBEDa 1s4 /m8 S4 − 0.025 98.6 100.1 97.5 A 9,39
TOQDEIa 0s4 /b4 m4 Irreg. 0.030 97.5 99.6 96.0 A 40
EHACOFa 1s24 /m4 S4 − 0.080 97.0 100.6 95.1 A 41,42
BEPBONa 1s4 /m8 S4 − 0.058 97.4 99.7 96.3 A 39
Published on 21 November 2006 on http://pubs.rsc.org | doi:10.1039/B614424A

MAWZUF 2s4 /m2 d D2 0.122 98.3 102.4 92.0 A 43

ZAHROP 0s4 /b4 m4 S4 − 0.023 97.4 99.0 96.5 A 44,45
MSALEN 0s4 /b4 m4 S4 − 0.015 97.7 97.3 98.7 A 46
DARPESa 1s24 /m4 S4 − 0.086 97.0 101.2 94.7 A 10
IBOGAI 0s4 /b2 d2 m4 S4 + 0.189 96.2 100.0 87.7 A 47
HUBZAFa 0s2 1s2s22/d2 m3 S4 + 0.130 97.4 101.2 89.5 B 48
TACNIH10 0s4 /t4 C3+ 0.012 99.0 98.7 99.6 B 49,50
YAQYAR 2s4 /m4 D2 0.072 99.0 102.7 95.6 B 51
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PAGXEA 0s4 /d4 m4 S4 − 0.075 98.3 103.3 95.9 B 52

Cobalt complexes

MAWZOZ 2s4 /m4 Irreg. 0.029 99.3 100.9 98.1 A 43

MAKFAG 0s4 /b4 m4 S4 − 0.046 97.1 99.3 95.8 A 21
JAXTOR 2s4 /m4 D2 0.012 99.0 99.8 98.0 A 22
UMUFOX 1s4 /d4 S4 − 0.133 96.6 104.1 92.7 B 53
ILUHUS 3s4 Irreg. 0.036 98.1 100.0 96.3 C 13
This work 2s122 3s2 Irreg. 0.121 98.4 108.2 94.1 C

Magnitude: degree of distortion as indicated by the e.s.d. of the metal–metal distances; M–O–M angles defined as the mean of the two angles linking a
pair of metals. a Indicates a system for which the average of two crystallographically independent molecules or two independent structure determinations
is given.

susceptibility data are available. We list in Table 4 the structural and
magnetic properties of the compounds found in the Cambridge
Structural Database for which magnetic data have been published.
For nickel compounds, many S4 -systems have been studied
and show, with one exception, type A behaviour. The exception,
PAGXEA,52 is unusual in that it has four diagonally bridging 2-
thionato-1,3-thiazoline ligands which may offer a supplementary
antiferromagnetic exchange pathway; this is also observed with
pivaloate ligands in the cobalt complex UMUFOX.53 EZIGAV,11
while formally a S4 + system, is only very slightly distorted and
all angles are less than 98◦ . The J values are therefore likely to
be very similar and ferromagnetic in nature. IBOGAI,47 while
the distribution of nickel–nickel distances corresponds to a S4 +
system, also has diagonally bridging pivaloate ligands resulting in
two very short Ni–Ni distances. This may account for the type A,
ferromagnetic behaviour. The S4 + system reported by Gladfelter
et al. shows the expected type B behaviour.54 It is harder to
predict the magnetic behaviour in less symmetric systems, since the
dependence of the J values on the M–O–M angle is not obvious.
In the case of [Co4 ((R,R)-1 − H)4 ](ClO4 )4 (C2 H5 OH)(H2 O)5 one
pair of cobalt atoms is linked by two bridges with angles of 96.8
and 108.2◦ and it seems reasonable to assume that the exchange
will be dominated by the antiferromagnetic coupling due to the
second: is it reasonable to take a mean value of 102.5◦ ?
For nickel complexes the data have generally been fitted to
a model incorporating a Heisenberg spin Hamiltonian, and for
temperatures below 20 K, a zero field splitting. Early work used a
single J value,9,40,45,55 but more recent work has used two or three
J values,10,37,38,43,47 thereby taking into account the distortion from
tetrahedral symmetry and leading to better fits. The fitted J values
show a correlation with the M–O–M angles although the scatter
is considerable. The cobalt complexes are more complicated by
virtue of the presence of unquenched orbital momentum, and con-
sequently first order spin–orbit coupling, and most authors have
limited themselves to a qualitative description of the behaviour.
However, in a study of a defect double cubane containing cobalt(II)
a simulation using a spin Hamiltonian adapted to the symmetry
and including an anisotropic term gave a qualitatively satisfactory
fit to data which resembled type C behaviour.56 At present it
seems unlikely that a useful magnetostructural correlation may be
established: the presence of many exchange constants in any but
the highest symmetry systems, coupled with the sensitivity of the
sign and magnitude of the J values to slight distortion makes their
prediction difficult, and the magnetic behaviour that is actually
observed depends in a complicated way on the relative values
of J.
1
H NMR spectroscopy
It is well established that polynuclear systems with exchange
coupling are often susceptible to study by NMR since the
exchange coupling creates new relaxation pathways, and if the

338 | Dalton Trans., 2007, 332–341 This journal is © The Royal Society of Chemistry 2007

relaxation is rapid enough, the paramagnetic broadening of the
1
H NMR spectrum is reduced to an acceptable level.57 We were
previously able to characterise polynuclear complexes of 1 with
copper(II) by NMR,3 and we have therefore recorded the NMR
spectra of [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 (H2 O)5 and [Co4 ((R,R)-1 −
H)4 ](ClO4 )4 (C2 H5 OH)(H2 O)5 as shown in Fig. 7.
Published on 21 November 2006 on http://pubs.rsc.org | doi:10.1039/B614424A
Downloaded by Duke University on 28 July 2012
Fig. 7 1 H NMR spectra of [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 (H2 O)5 (top) and
[Co4 ((R,R)-1 − H)4 ](CIO4 )4 (C2 H5 OH)(H2 O)5 (bottom) in acetonitrile at
293 K (* solvent peak, ◦ H2 O peak, ? tentative signal assignment).
The spectrum of the nickel complex is in agreement with the
crystal structure of the cobalt complex. The aromatic protons
were identified by their coupling from a COSY spectrum where
four sets of three coupled protons were identified. The failure
to observe the fourth proton of the benzimidazole presumably
arises from its proximity to the paramagnetic centre, paramagnetic
broadening precluding the observation of a COSY signal, as found
in the copper(II) systems. The missing aromatic peaks may be
the broadened signals in the region 17–21 ppm. In the spectrum
shown, only three methyl resonances are visible, but the fourth is
hidden by the solvent and residual water peak. Recording the
spectrum in DMSO and varying the temperature allowed the
fourth methyl signal to be shifted out of this peak. The observation
of four methyl and four benzimidazole signals is consistent with
a structure [Ni4 ((S,S)-1 − H)4 ]4+ having C 2 symmetry as observed
in the crystal structure of the cobalt complex.
The spectrum of the cobalt complex is harder to understand,
since there is clearly more than one species present. The majority
species shows six signals for the aromatic protons of the benz-
imidazoles (identified as above by the COSY spectrum) and two
methyl resonances, corresponding to two different environments
for benzimidazoles. There are three weak resonances above 50 ppm
and three more below −20 ppm. The ESMS suggests strongly
that [Co4 ((R,R)-1 − H)4 ]4+ is the majority species in solutions
under these conditions, and the UV-visible spectrum is quite
similar to that observed for the crystalline solid. We therefore
consider [Co4 ((R,R)-1 − H)4 ]4+ to be the major species present. The
observation of two different environments requires the symmetry
of the species in solution to be higher than that observed in the
solid, and that observed for [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 (H2 O)5 .
This journal is © The Royal Society of Chemistry 2007
View Online
This could arise from a change in structure but could equally arise
from a dynamic effect since the cobalt(II) centre is much more
labile than the nickel.
Conclusions
We have shown that ligand 1 which we had previously shown
to form tetranuclear clusters with copper(II) can also form such
complexes with cobalt(II) and nickel, using the second, unpro-
tonated, diol function to complete the octahedral coordination
of the metal ion. This implies quite considerable conformational
flexibility on the part of the ligand. The structure is significantly
distorted from the tetrahedral ideal, but not more so than
other complexes in the literature. Analysis of the data in the
literature suggests that the M4 O4 has rather constant structure
for a given M and oxidation state, and that in the majority of
cases the distortion maintains some elements of the tetrahedral
symmetry, most commonly the S4 axis. Although the sign of the
magnetic exchange parameters J appears to depend on the M–
O–M angle, the magnetic properties observed for the complex as
a whole depend on the interaction of several exchange pathways,
both ferromagnetic and antiferromagnetic, and are not readily
predicted.
Experimental
Safety note
Although no problems were experienced in handling perchlorate
compounds, these salts are potentially explosive when combined
with organic ligands. The compounds should be handled with care,
and only used in small quantities.
General
Starting materials were purchased commercially, and were used
as supplied unless specified otherwise. Ligand 1 was prepared in
both enantiomeric forms as described previously.4 Proton NMR
spectra were recorded at 300 MHz on a Varian Gemini instrument.
Infrared spectra were recorded as KBr discs on a Perkin-Elmer
Spectrum One spectrometer. UV/vis spectra were recorded using
a Perkin-Elmer Lambda 900 UV/vis/NIR machine; reflectivity
spectra used the same instrument equipped with a 60 mm
integration sphere. The white standard was PTFE. Samples were
prepared in a 1 mm cell after mixing the compound with roughly
nine times the amount of MgO. CD spectra were recorded on a
Jasco J-15 spectrometer.
Magnetic susceptibility data were collected with a Quantum
Design SQUID magnetometer (XL5S) operating in the range
300–2 K with a field of 1000 G. The data were corrected for
sample holder contribution (saran foil) and for the diamagnetic
contribution estimated using Pascal’s constants.58
Synthesis of complexes
Tetrakis((R,R)-1,2-1H -benzimidazol-2-yl)ethanediolate)tetra-
cobalt(II) tetraperchlorate–ethanol solvate, [Co4 ((R,R)-1 − H)4 ]-
(ClO4 )4 (C2 H5 OH)(H2 O)4 .
Method (a).A mixture of Co(ClO4 )2 ·6H2 O (0.0732 g, 0.2 mmol)
and (R,R)-1 (0.0644 g, 0.2 mmol) was dissolved in 10 ml hot
Dalton Trans., 2007, 332–341 | 339

ethanol. After adding one equivalent sodium hydroxide (200 ll
NaOH 1 M, 0.2 mmol) a rose precipitate is formed. The precipitate
could be redissolved by adding 1 ml water. Diffusion of ethanol
via the gas phase led to formation of rose crystals within one day.
The solution was filtered after two weeks and the crystals air dried
(0.050 g, 43%).
Method (a1). The synthesis was carried out as described in (a),
but 1.5 ml water were added to dissolve the rose precipitate and
crystals started growing within one week. Monocrystals suitable
for X-ray structure analysis were obtained.
Method (b). A mixture of Co(ClO4 )2 ·6H2 O (0.0366 g,
0.1 mmol) and (R,R)-1 (0.0322 g, 0.1 mmol) was dissolved in 8 ml
Published on 21 November 2006 on http://pubs.rsc.org | doi:10.1039/B614424A
hot ethanol. After adding two equivalents of 2,5-dimethylpyridine
(232 ll 96%, 0.2 mmol) a rose precipitate formed. The precipitate
transformed within three weeks into crystals. Heat accelerates
this process. The solution was filtered and the crystals air dried
(0.0430 g, 74%). It was observed that the crystals readily lost
solvent, and the composition of the air-dried sample is thus
different from the crystals used for X-ray diffraction studies,
Downloaded by Duke University on 28 July 2012
where care was taken to avoid solvent loss. Solubility: soluble
in DMSO, acetonitrile, acetone and a water–ethanol mixture
(1 : 9); less soluble in methanol; insoluble in ethanol, water,
ethanol–water mixture (1 : 1), chloroform, and tert-butyl methyl
ether. Elemental analysis: Found : C, 43.2; H, 4.2; N, 10.8%;
C72 H68 N16 O8 ·4Co·4ClO4 ·5H2 O·C2 H5 OH requires C, 43.3; H, 4.1;
N, 10.9%; UV-visible (T = 22 ◦ C, c = 0.015 M (CH3 CN)) kmax /nm
(e/dm3 mol−1 cm−1 ): 460 (50), 527 (sh) (62), 560 (76), 704 (9),
1044 (8); CD (T = 22 ◦ C, c = 0.015 M (CH3 CN)) kmax /nm
(De/dm3 mol−1 cm−1 ) : 450 (−0.528), 480 (sh) (0.4701), 515 (1.487),
553 (−0553), 702 (−0.613); reflectivity spectrum: in MgO kmin /nm:
480 (sh), 542, 682, 1054; IR (KBr) m/cm−1 : 3414br m, 3060w,
2947w, 2656w, 2022w, 1616m, 1497m, 1483m, 1457s, 1408m,
1318m, 1294m, 1278m, 1247w, 1087br s, 1010w, 970w, 924m,
898m, 876m, 876m, 804w, 744s, 680w, 625s, 591w, 565w, 548w,
537w, 485m, 404w, 353w. ESMS (CH3 CN): m/z (%) = 759.2(100)
[Co4 (1)4 (−6H)]2+ , 520.2 (38) [Co4 (1)4 (−5H)(CH3 CN)]3+ , 506.5
(16) [Co4 (1)4 (−5H)]3+ , 816.1 (7) [Co3 (1)2 (−5H)]+ , 1516.8 (3)
[Co4 (1)4 (−7H)]+ . 1 H NMR (? unassigned peaks or tentative
assignment) (T = 22 ◦ C, c = 0.0428 M (CD3 CN), 300 MHz):
primary species (probably [Co4 (1 − H)4 ]4+ ), only the eight sharpest
signals are listed with their tentative signal assignment: d (ppm):
39.10 (aHarom ?, s), 23.38 (1Harom ?, s), 18.27 (1Harom ?, s), 10.56
(1Harom ?, s), 5.90 (3H, CH3 , s), −9.81 (1Harom ?, s), −13.30 (1Harom ?,
s), −16.85 (3H, CH3 , s). Unassigned signals due to the primary
species and one or two secondary species: d(ppm): 99.82 (s, br),
83.72 (s, br), 74.75 (s, br), 64.34 (s, br), 63.33 (s, br), 44.12 (s),
39.09 (s), 27.28 (s), 24.52 (s), 17.63 (s), 11.81 (s), 4.08 (s), 3.51
(s), 2.84 (s), 0.67 (s), −0.67 (s), −3.22 (s), −8.44 (s), −33.66 (s),
−54.05 (s, br), −79.70 (s, br). (HH) COSY (with gradient selection,
500 MHz, Bruker), cross peaks (ppm): 39.10/18.27, 10.56/9.81,
−9.81/13.30.
Tetrakis((S,S) - 1,2 - 1H - benzimidazol - 2 - yl)ethanediolate)tetra-
nickel(II) tetraperchlorate hydrate, [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 -
(H2 O)5 . A mixture of Ni(ClO4 )2 ·6H2 O (0.0366 g, 0.1 mmol) and
(S,S)-1 (0.0322 g, 0.1 mmol) was dissolved in 10 ml ethanol.
On adding one equivalent 2,5-dimethylpyridine (117 ll, 96%)
the colour of the solution turned from turquoise to green.
A green microcrystalline precipitate formed immediately, which
340 | Dalton Trans., 2007, 332–341
View Online
transformed within a week to green crystals in form of thin sheets.
The solution was filtered off and the crystals dried in vacuum
(0.0392 g, 77%). Solubility: soluble in DMSO, acetonitrile, acetone
and nitromethane, less soluble in methanol, insoluble in water,
ethanol and chloroform. Elemental analysis: Found: C, 43.2; H,
4.1; N, 11.0%; C72 H68 N16 O8 [Ni4 ((S,S)-1 − H)4 ](ClO4 )4 (H2 O)5
requires C, 43.1; H, 3.9; N, 11.2%. UV-visible (T = 22 ◦ C, c =
0.00983 M (CH3 CN)) kmax /nm (e/dm3 mol−1 cm−1 ) : 402 (31), 662
(13), 763 (sh) (7), 1135 (10); CD (T = 22 ◦ C, c = 0.00983 M
(CH3 CN)) kmax /nm (De/dm3 mol−1 cm−1 ) : 414 (−0.236), 663
(−0.204), 746 (−0.166); reflectivity in MgO kmin /nm: 399, 660, 763
(sh), 1155 (broad band low in intensity); IR (KBr) m/cm−1 : 3416br
m; 3059w, 1617m, 1500m, 1481m, 1458m, 1412w, 1336m, 1318m,
1295m, 1276m, 1086br s; 1010w, 925m, 903m, 877m, 804w, 746m,
679w, 626m, 582w, 554w, 539w, 501w; ESMS (CH3 CN): m/z (%) =
758.3 (100) [Ni4 (1)4 (−6H)]2+ , 506.0 (8) [Ni4 (1)4 (−5H)]3+ , 1617.0 (8)
[Ni4 (1)4 (−6H)(ClO4 )]+ , 519.6 (7) [Ni4 (1)4 (−5H)(CH3 CN)]3+ , 809.2
(6) [Ni4 (1)4 (−5H)(ClO4 )]2+ ; 1 H NMR (assignment not complete,
? not assigned peaks) (T = 22 ◦ C, CD3 CN, 300 MHz: d (ppm))
29.82 (1Harom , s), 29.77 (1Harom , s), 25.17 (1Harom , s), 23.30 (1Harom ,
s), 20.68 (1H br, ?), 17.14 (2H br, ?), 13.66 (1H br, ?), 10.16 (1Harom ,
s), 9.60 (1Harom , s), 8.65 (1Harom , s), 8.55 (1Harom , s), 7.47 (1Harom , s),
7.03 (1Harom , s), 6.11 (1Harom , s), 5.62 (1Harom , s), 4.22 (3H, CH3 , s),
2.66 (3H, CH3 , s), −0.83 (3H, CH3 , s). (H,H) COSY (300 MHz,
Varian Gemini 300), cross peaks (ppm): 29.82/8.55, 8.55/10.16,
29.77/8.65, 8.65/9.60, 25.17/6.11, 6.11/7.03, 23.30/–5.62, 5.62/–
7.47.
Crystal structure determination of [Co4 ((R,R)-1 − H)4 ](ClO4 )4 -
(C2 H6 O)9 . Crystals were obtained by vapour diffusion of ethanol
into an aqueous ethanol solution of the complex. Crystal data:
Co4 (C18 H17 N4 O2 )4 (ClO4 )4 (C2 H6 O)9 , M = 2333.8, orthorhombic,
space group C2221 , a = 19.1066(12), b = 23.3433(10), c =
23.6269(17) Å, U = 10538(1) Å3 , T = 200 K, Z = 4, l(Mo-Ka) =
0.81 mm−1 , 66 435 reflections measured (Stoe IPDS), 10 276 unique
(Rint. = 0.069), 5838 observed (|F o | > 4r(F o )). Final R value
0.037 (wR = 0.037) for 663 variables, absolute structure (Flack)59
parameter x = −0.01(2). The structure was solved using direct
methods (MULTAN-8760 ), and other calculations used XTAL
3.261 and ORTEP-II62 programmes. The hydrogens of OH groups
were not observed.
CCDC reference number 622954.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b614424a
Acknowledgements
We gratefully acknowledge the support of this work by the Swiss
National Science Foundation.
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